Modified propylene polymer, composition containing the same and use thereof

ABSTRACT

This invention provides a graft modified polypropylene polymer which does not contain halogens, is excellent in certain properties such as solubility and can add good adhesiveness and coating ability to crystalline propylene polymer base materials, and a composition containing the same; and in particular, it provides a propylene polymer which contains a propylene polymer main chain having a stereo-block structure containing an isotactic block and a side chain containing a carboxylic acid group, an acid anhydride group or a carboxylic acid ester group, wherein when it is dissolved in toluene to a concentration of 10% by weight at 25° C., the insoluble matter is 1% by weight or less based on the total polymer, and a composition containing the same.

FIELD OF THE INVENTION

This invention relates to a novel propylene polymer. Moreillustratively, it relates to a propylene polymer which has goodsolubility in organic solvents such as toluene and is used as materialssuch as finishing agents, adhesives and paints particularly for olefinpolymers having crystallinity, particularly to a graft modifiedpropylene polymer and an adhesive composition containing this polymer.

BACKGROUND OF THE INVENTION

Propylene polymers and propylene-α-olefin copolymers are used in broadfields, because they are inexpensive and have superior properties suchas mechanical property, heat resistance, solvent resistance and waterresistance. However, such propylene polymers generally have low polaritybecause of the absence of polar groups in their molecules, thus posing adisadvantage of being difficult to effect coating and adhesion. In orderto improve this disadvantage, various techniques have been attempted,such as chemical treatment of the surface of moldings of these propylenepolymers with solvents and oxidation treatment of the surface ofmoldings by techniques such as corona discharge treatment, plasmatreatment and flame treatment. However, these methods require specialapparatus, and it cannot be said that their effects to improve coatingproperty and adhesiveness are sufficient.

Accordingly, a so-called chlorinated polypropylene has been developed asa device for adding good coating ability and adhesiveness to propylenepolymers by a relatively convenient method. The chlorinatedpolypropylene is generally soluble in hydrocarbon solvents such astoluene and xylene and, what is more, its adhesiveness to base materialssuch as propylene polymers is relatively good. Thus, coating ability andadhesiveness of propylene polymers can be improved by a relativelysimple method in which a hydrocarbon solution of the chlorinatedpolypropylene is coated on the surface of a propylene polymer to be usedas the base material and then the solvent is removed. In thisconnection, it is known that a modified chlorinated polypropyleneobtained by further modifying the chlorinated polypropylene by graftcopolymerization of a polar monomer has further superior effect toimprove coating ability and adhesiveness.

Accordingly, though coating ability and adhesiveness of propylenepolymers can be improved relatively conveniently using the chlorinatedpolypropylene or modified chlorinated polypropylene, there is a problemof containing chlorine in a large amount. In recent years, the use ofvinyl chloride resins is causing a social problem due to possiblegeneration of toxic substances by inadequate incineration of the resins,and the chlorine-containing resins also have problems remained unsolvedsuch as poor weather resistance. Thus, great concern has been directedtoward the development of a substitute resin for chlorinatedpolypropylene as in the case of vinyl chloride resins, which does notcontain halogens such as chlorine.

In view of such background, on the other hand, development of a resincontaining no chlorine has been attempted. For example, Japanese PatentPublication No. 958/1969 discloses a treating agent in which anamorphous polypropylene polymer modified with a specified ratio ofmaleic acid or its anhydride is dissolved in a solvent. In this case,the amorphous polypropylene polymer is an amorphous polymer whichcontains at least about 20 mol % of propylene unit in atacticpolypropylene and copolymer as occasion demands and comprises acopolymer of at least one comonomer and propylene. Also, as a similartreating agent, Japanese Patent Laid-Open No. 217835/1996 discloses anamorphous polymer in which unsaturated carboxylic acids having from 3 to10 carbon atoms are graft-copolymerized with an amorphous polypropyleneor amorphous propylene-1-butene copolymer. When such a graft modifiedpolymer is used, it has improved solubility and superior coating abilityin comparison with general modified propylene resins, but it still haslow solubility in solvents at room temperature, shows stickiness, and ispoor in adhesiveness. Thus, for the purpose of using as a finishingagent, an adhesive or a paint, it is considered that the chlorinatedpolypropylene or modified chlorinated polypropylene is a relativelyexcellent resin at present.

SUMMARY OF THE INVENTION

An object of this invention is to provide a novel propylene polymer,particularly a graft modified propylene polymer and a compositioncontaining the same which do not contain halogens such as chlorine, haveno stickiness and excellent in solubility, and can add good adhesivenessand coating ability to base materials such as crystalline propylenepolymers.

With the aim of solving the problems involved in the art, the presentinventors have conducted intensive studies and accomplished theinvention as a result of the efforts.

Accordingly, the gist of the invention resides in a propylene polymerwhich comprises a propylene polymer main chain having a stereo-blockstructure containing an isotactic block and a side chain containing acarboxylic acid group, an acid anhydride group or a carboxylic acidester group (to be generally referred to as carboxylic acid grouphereinafter), wherein when it is dissolved in toluene to a concentrationof 10% by weight at 25° C., the insoluble matter is 1% by weight or lessbased on the total polymer; a propylene polymer having characteristics(a) and (b), (a) when it is dissolved in toluene to a concentration of10% by weight at 25° C., the insoluble matter is 1% by weight or lessbased on the total polymer, (b) its adhesiveness by an adhesion test(cross-cut tape method) to a polypropylene base material is 50/100 ormore; and an adhesive composition which contains the propylene polymer.

Other objects and advantages of the invention will be made apparent asthe description progresses.

DETAILED DESCRIPTION OF THE INVENTION

In the propylene polymer of the invention, a propylene polymer mainchain having a stereo-block structure containing an isotactic block (tobe referred sometimes to as propylene polymer main chain hereinafter) isgraft-copolymerized with a polymerizable monomer containing a carboxylgroup. This propylene polymer main chain is a propylene homopolymer or apropylene-ethylene copolymer, whose ethylene content is less than 5weight %. The propylene polymer main chain comprises propylene [P] withthe proportion of 95<[P]≦100 (weight %) and ethylene [E] with theproportion of 5>[E]≧0 (weight %), but it may contain a small amount ofother comonomer components within such a range that they do not spoilthe scope of the invention.

Other suitable comonomers which can be contained in the propylenepolymer main chain can be selected from the group of monomers having atleast one olefinic double bond, such as butene, pentene, hexene, octene,decene, butadiene, hexadiene, octadiene, cyclobutene, cyclepentene,cyclohexene, norbornene, norbornadiene, styrene and derivatives thereof.Among them, butene, pentene, hexene and octene are preferable, andbutene is more preferable.

Ethylene content [E] (mol %) can be calculated as the average value of(1) the etylene content computed by α-methylene method and (2) theetylene content computed by β-methylene method, which can be measured by¹³C-NMR method described later.

The value of ethylene content thus obtained has the unit of “mol %”, andit can be easily converted to the value with the unit of “weight %” byusing molecular weight of ethylene and propylene.

α-methylene  method[CH]_(α) = T_(A) + (T_(C) + T_(D))/2[CH₂]_(α) = T_(A) + 2T_(C) + T_(D) + T_(F3 − 5) − T_(I)[C2]_(α) = ([CH₂]_(α) − [CH]_(α))/([CH₂]_(α) + [CH]_(α))β-methylene  method[CH]_(β) = T_(A) + (T_(H) + 2T_(I) + T_(D))/2[CH₂]_(β) = T_(A) + T_(D) + T_(F3 − 5) + 2T_(H) + 3T_(I)[C2]_(β) = ([CH₂]_(β) − [CH]_(β))/([CH₂]_(β) + [CH]_(β))content  of  ethylene = ([C2]_(α) + [C2]_(β))/2 T_(C) = ∑I(37.2 − 39.2)T_(D) = ∑I(34.8 − 36.2) T_(F3 − 5) = ∑I(29.5 − 30.9)T_(H) = ∑I(26.9 − 28.0) T_(I) = ∑I(24.3 − 25.2)wherein I(a-b) means the integrated peak area between the chemical shiftof a (ppm) and b (ppm) on ¹³C-NMR spectrum.

Also, when the ethylene content in the propylene polymer main chain isvery small, the following value calculated by the following method hashigher accuracy.

${{C2}\left( {{mol}\%} \right)} = \frac{{\sum{I\left( {24.5 - 25.0} \right)}} + {\sum{I\left( {33.5 - 34.2} \right)}}}{\begin{matrix}{{\sum{I\left( {24.5 - 25.0} \right)}} + {\sum{I\left( {33.5 - 34.2} \right)}} +} \\{{\sum{I\left( {14.2 - 23.5} \right)}} + {\frac{1}{2}{\sum{I\left( {27.5 - 28.0} \right)}}}}\end{matrix}}$

As the method for controlling the ethylene content [E] in the range of0≦[E]<5 (weight %), adjusting the feed ratio of the propylene andethylene for polymerization is most practical.

The ratio of propylene and ethylene can not be particularly pointed outbecause the results depend on the catalyst to be used. One can determinein advance the preferable feed ratio by preliminary examinations varyingthe feed ratio and seeing how the content changes with the catalysts tobe used, and with the conditions such as pressure and temperature.

In case the content of ethylene exceeds 5 (weight %) the solubility ofobtained propylene polymer main chain in solvents increases, while ittends to show poor non-tackiness and adhesiveness, and is not desirable.

It is essential that the propylene polymer main chain of the inventionhas a stereo-block structure containing an isotactic block, and it isdesirable that it has a weight average molecular weight Mw of from 5,000to 200,000 when measured by GPC (gel permeation chromatography). The Mwsmaller than 5,000 is not desirable, because not only worsening of filmforming ability becomes significant but stickiness also becomessignificant after coating on a base material using a propylene polymermodified by graft copolymerization (to be referred sometimes to as graftmodified polymer hereinafter). Also, the Mw exceeding 200,000 is notdesirable because, though there are no big problems regarding the filmforming ability and stickiness, viscosity becomes too high when thegraft modified polymer is dissolved in a solvent, thus causing aninconvenience in view of the production or handling of the graftmodified polymer solution. According to the invention, the weightaverage molecular weight Mw is within the range of preferably from 5,000to 200,000, but more preferably from 10,000 to 180,000 and mostpreferably from 30,000 to 150,000.

In this connection, measurement of molecular weight by GPC can becarried out by a conventionally known method using commerciallyavailable apparatus, a solvent such as o-dichlorobenzene and polystyreneas the standard sample.

Regarding molecular weight distribution of the propylene polymer mainchain of the invention, there is no particular limitation, but too broadmolecular weight distribution should be avoided because it meansinevitably large content of low molecular weight components. When theratio of weight average molecular weight Mw to number average molecularweight Mn, Mw/Mn, is used as an index of the molecular weightdistribution, it is preferably Mw/Mn<20, more preferably Mw/Mn<10, mostpreferably Mw/Mn<5.

As described above, the propylene polymer main chain of the inventionhas a stereo-block structure containing an isotactic block, and thosewhich are produced using a specific catalyst and have smallerheptane-insoluble matter are desirable. Particularly, those which havethe characteristic defined as described in the foregoing by ¹³C-NMRspectrum are more desirable. This characteristic means that a blockhaving high crystallinity and a block having high amorphous property arepresent in the propylene polymer main chain in good balance, and thatthe block having high crystallinity is in a structure rich in isotacticproperty. That is, since solubility in a solvent worsens when the ratioof a block having high crystallinity being present in the polymer mainchain is too large, balance of the block having high crystallinity andthe block having high amorphous property becomes important, and therequirement defined by ¹³C-NMR spectrum is applied as a part of indexesrepresenting this balance.

The method for measuring ¹³C-NMR spectrum in the invention is asfollows.

A 350 to 500 mg portion of a sample is completely dissolved using about2.2 ml of o-dichlorobenzene in a 10 mm φ NMR sample tube. Next, this ishomogenized by adding about 0.2 ml of benzene deuteride as a locksolvent, and then the measurement is carried out at 130° C. by a protoncomplete decoupling method. The measuring conditions are set to a flipangle of 90° and a pulse interval of 5T₁ or more (T₁ is the longestvalue among spin-lattice relaxation times of methyl group). Sincespin-lattice relaxation times of methylene group and methine group areshorter than those of methyl group, recovery of magnetization of allcarbons is 99% or more. In this connection, in order to improvedetermination accuracy, it is desirable to use an NMR apparatus of 125MHz or more as the ¹³C nuclear resonance frequency and carryout-integration for 20 hours or more.

Regarding the chemical shift, among 10 kinds of pentads of the propyleneunit chain region comprising a head to tail bond (mmmm, mmmr, rmmr,mmrr, ummm, rmrr, rmrm, rrrr, rrrm and mrrm), chemical shift of a peakbased on the third unit methyl group of five continuous propylene unitsin which all of the methyl branch absolute configurations are identical,namely, the pentad represented by mmmm, is set at 21.8 ppm, and chemicalshifts of other carbon peaks are determined using this as the standard.According to this standard, in the case of other five continuouspropylene units, for example, chemical shift of a peak based on thethird unit methyl group roughly becomes as follows. That is, mmmr: 21.5to 21.7 ppm, rmmr: 21.3 to 21.5 ppm, mmrr: 21.0 to 21.1 ppm, mmrm andrmrr: 20.8 to 21.0 ppm, rmrm: 20.6 to 20.8 ppm, rrrr: 20.3 to 20.5 ppm,rrrm: 20.1 to 20.3 ppm and mrrm: 19.9 to 20.1 ppm. In this connection,it is necessary to carry out the assignment by taking into considerationthat chemical shifts of peaks originated from these pentads slightlyvary depending on the NMR measuring conditions and that each peak is notalways a single peak but shows a complex split pattern in many casesbased on the fine structure.

Regarding the propylene polymer main chain of the invention, it isdesirable that when chemical shift of the peak top of a peak assignedfor a pentad represented by mmmm is defined as 21.8 ppm, the ratio(S₁/S) of area S₁ of a peak having a peak top of 21.8 ppm to the totalarea S of peaks of the pentads appeared within the range of from 19.8ppm to 22.2 ppm, namely peaks assigned for all pentads of mmmm, mmmr,rmmr, mmrr, mmrm, rmrr, rmrm, rrrr, rrrm and mrrm, is 10% or more and60% or less, and that when area of a peak having a peak top of 21.5 to21.7 ppm (mmmr) is defined as S₂, 4+2S₁/S₂>5.

According to a preferred propylene polymer main chain of the invention,ratio of the area of a peak assigned for a specified pentad to the totalarea (S) of peaks of the all pentads appeared within 19.8 ppm to 22.2ppm satisfies the following requirements (1) to (4). In this case, %represents ratio of the area of a peak assigned for a specified pentadto the total area of peaks of the all pentads appeared within 19.8 ppmto 22.2 ppm.

(1) When area of a peak having a peak top of 20.3 to 20.5 ppm (rrrr) isdefined as S₃, ratio of the area S₃ (S₃/S) is 0.2% or more and 3% orless,

(2) when area of a peak having a peak top of 20.6 to 20.8 ppm (rmrm) isdefined as S₄, ratio of the area S₄ (S₄/S) is 0.3% or more and 7% orless,

(3) the area of S₄ is larger than the area of S₃, and

(4) the area of S₂ is 25>4+2S₁/S₂>5.

A more preferred propylene polymer main chain satisfies the followingrequirements (1) to (4) (wherein S and S₁ to S₄ are as defined in theforegoing).

(1) Ratio of the area S₁ (S₁/S) is 30% or more and 50% or less,

(2) ratio of the area S₃ (S₃/S) is 1% or more and 3% or less,

(3) ratio of the area S₄ (S₄/S) is 4% or more and 7% or less,

(4) the area of S₂ is 10>4+2S₁/S₂>7.

Among these requirements, each of the requirements (1) to (3) is relatedto the facts that a block having high crystallinity and a block havinghigh amorphous property are present in the propylene polymer main chainof the invention, and that the block having high crystallinity is in astructure rich in isotactic property. In this connection, when the ratioof S₁ to S is less than 10%, it is not desirable because sufficientadhesiveness cannot be obtained due to too low crystallinity and it isapt to cause problems such as stickiness. On the other hand, when theratio of S₁ to S exceeds 60%, it also is not desirable becausesolubility in a solvent is reduced due to too high crystallinity. Rangeof the ratio of S₁ to S defined in the invention is 10% or more and 60%or less, but is preferably 20% or more and 50% or less and morepreferably 30% or more and 50% or less.

It is desirable that the propylene polymer main chain of the inventionsatisfies the relationship of 4+2S₁/S₂>5. This relational expression hasa close relation to an index named by Waymouth et al. as isotactic blockindex (BI) (cf. Unexamined International Patent Publication No.510745/1997). The BI is an index showing stereo-block property ofpolymers and defined by BI=4+2 [mmmm]/[mmmr]. More illustratively, BIrepresents average chain length of an isotactic block having 4 or morepropylene units (J. W. Collete et al., Macromol., 22, 3858 (1989); J. C.Randall, J. Polym. Sci. Polym. Phys. Ed., 14, 2083 (1976)). In the caseof a statistically complete atactic polypropylene, it becomes BI=5.Accordingly, BI=4+2 [mmmm]/[mmmr]>5 means that average chain length ofisotactic block is longer than that of atactic polypropylene.

The formula 4+2S₁/S₂ as a requirement of the propylene polymer mainchain of the invention is not completely identical to the BI but roughlycorresponds thereto, so that the requirement 4+2S₁/S₂>5 means that,different from atactic polypropylene, main chain of the propylenepolymer of the invention contains an isotactic block having acrystallizable chain length. Also, the presence of an isotactic blockmeans in other words that a block comprising a sequence having turbulentstereospecificity is simultaneously present in the main chain. Thus, asdescribed in the foregoing, the propylene polymer main chain of theinvention has a unique structure in which a block having highcrystallinity and a block having high amorphous property are present inthe main chain, and the block having high crystallinity is formed froman isotactic block having a relatively long average chain length so thatit is in a structure rich in isotactic property.

According to the invention, it may be 5<4+2S₁/S₂, but is preferably5<4+2S₁/S₂<25, more preferably 7<4+2S₁/S₂<10.

In addition, since the propylene polymer main chain of the invention hassuitable stereoregularity distribution of methyl group in the polymermain chain, it has a characteristic in that it has good solubility in asolvent because its crystallinity is also relatively low.Illustratively, it is a characteristic that substantially all componentsare eluted at 60° C. or less when the polymer main chain is subjected totemperature rising elution fractionation with o-dichlorobenzene. Sincethe components eluted at a temperature of higher than 60° C. arecomponents having markedly high crystallinity, in case that the polymermain chain contains such components, it is apt to cause inconvenienceswhen the polymer main chain is dissolved in a solvent, such as formationof insoluble matter from such components having high crystallinity andgeneration of gelation. Since substantially all components of thepropylene polymer main chain of the invention are eluted at 60° C. orless, such inconveniences can be avoided, but it is desirable thatsubstantially all components are eluted at preferably 50° C. or less,more preferably at 40° C. or less.

The propylene polymer main chain of the invention is obtained by amethod in which it is polymerized using a single site catalyst. Examplesof the reason for this include that microtacticity can be controlled bydesigning the ligand, a polymer having relatively low molecular weightcan be easily produced and particularly molecular weight distributionand stereoregularity distribution of the polymer are sharp. Whenmolecular weight distribution and stereoregularity distribution areirregular, there is a possibility that insoluble matter is partiallyformed due to difference in solubility. Among single site catalysts, ametallocene catalyst is suitably used from the viewpoint that it canprecisely control microtacticity.

As the single site catalyst for use in the production of the propylenepolymer main chain of the invention, a metallocene catalyst containing ametallocene compound ([A] component) and a co-catalyst ([B] component)as essential components is desirably used.

As the metallocene compound ([A] component), a C₁-symmetricansa-metallocene having a transition metal-containing bridge group isdesirable. Though a non-bridge metallocene can also be applied to theproduction of the propylene polymer of the invention, anansa-metallocene having a bridge group is generally desirableparticularly from the industrial point of view because of its excellentproperties such as heat stability.

The ansa-metallocene to be used in the invention having a transitionmetal-containing bridge group is a C₁-symmetric metallocene of acrosslinked group IV transition metal compound having a conjugatedfive-membered ring ligand. Such a transition metal compound is wellknown, and it is known that this is used as an α-olefin polymerizationcatalyst component.

The metallocene of [A] component desirably used for the production ofpropylene polymer is a compound represented by the following generalformula (I) and having C₁-symmetry. Also, two or more metallocenecompounds represented by this general formula may be used as a mixture.Q(C₅H_(4-a)R² _(a))(C₅H_(4-b)R³ _(b))MXY  (I)

The metallocene having this general formula is described in detail inthe following.

In the general formula (I), Q represents a binding group which bridgesbetween two conjugated five-membered ring ligands, M represents a groupIV transition metal of the periodic table, X and Y each independentlyrepresents hydrogen, a halogen, a hydrocarbon group having from 1 to 20carbon atoms, an oxygen-containing hydrocarbon group having from 1 to 20carbon atoms, a nitrogen-containing hydrocarbon group having from 1 to20 carbon atoms, a phosphorus-containing hydrocarbon group having from 1to 20 carbon atoms or a silicon-containing hydrocarbon group having from1 to 20 carbon atoms, and R² and R³ each independently represents ahydrocarbon group having from 1 to 20 carbon atoms, a halogen, ahalogen-containing hydrocarbon group having from 1 to 20 carbon atoms,an alkoxy group, an aryloxy group, a silicon-containing hydrocarbongroup, a phosphorus-containing hydrocarbon group, a nitrogen-containinghydrocarbon group or a boron-containing hydrocarbon group. Also,adjacent two R² and/or R³ may be respectively bonded to form a four- toten-membered ring. The symbols a and b are each independently an integerwhich satisfies 0≦a≦4 or 0≦b≦4.

As the binding group Q which bridges between two conjugatedfive-membered ring ligands, the following can be cited as illustrativeexamples. That is, alkylene groups such as methylene and ethylene,alkylidene groups such as ethylidene, propylidene, isopropylidene,phenylmethylidene and diphenylmethylidene, silicon-containing bridgegroups such as dimethylsilylene, diethylsilylene, dipropylsilylene,diphenylsilylene, methylethylsilylene, methylphenylsilylene,methyl-t-butylsilylene, disilylene and tetramethyldisilylene andgermanium-containing bridge groups such as dimethylgermilene,diethylgermilene, diphenylgermilene and methylphenylgermilene, as wellas alkylphosphines and amines. Among them, alkylene groups, alkylidenegroups, silicon-containing bridge groups and germanium-containing bridgegroups are particularly desirably used.

Illustrative examples of R² and R³ in the general formula (I) includehydrocarbon groups having from 1 to 20 carbon atoms which may besubstituted, such as methyl, ethyl, n-propyl, isopropyl, n-butyl,isobutyl, t-butyl, n-pentyl, isopentyl, cyclopentyl, hexyl, cyclohexyl,heptyl, octyl, nonyl, decyl, phenyl, t-butylphenyl and naphthyl,hydrocarbon groups having from 1 to 20 carbon atoms which may containhalogen, such as fluoromethyl, fluoroethyl, fluorophenyl,fluoronaphthyl, fluorobiphenyl, chloromethyl, chloroethyl, chlorophenyl,chloronaphthyl and chlorobiphenyl, halogen atoms such as fluorine,chlorine, bromine and iodine, alkoxy groups such as methoxy, ethoxy,propoxy and butoxy, aryloxy groups such as phenoxy, methylphenoxy andpentamethylphenoxy, silicon-containing hydrocarbon groups such astrimethylsilyl, triethylsilyl and triphenylsilyl, phosphorus-containinghydrocarbon groups, nitrogen-containing hydrocarbon groups andboron-containing hydrocarbon groups. When two or more of R² are present,they may be the same or different from one another.

Also, when two of R² are present on adjacent carbon atoms ofcyclopentadienyl ring, they may be mutually bonded to form a four- toten-membered ring group such as indenyl, tetrahydroindenyl, fluorenyl,octahydrofluorenyl, azulenyl or hexahydroazulenyl. In the same manner,when two or more of R³ are present, they may be the same or differentfrom one another. In addition, when two of R³ are present on adjacentcarbon atoms of cyclopentadienyl ring, they may be mutually bonded toform a four- to ten-membered ring group such as indenyl,tetrahydroindenyl, fluorenyl, octahydrofluorenyl, azulenyl orhexahydroazulenyl.

According to the invention, the metallocene represented by the generalformula (I), Q(C₅H_(4-a)R² _(a))(C₅H_(4-b)R³ _(b))MXY, has C₁-symmetry,so that R² and R³ may be the same or different from each other so far asthe C₁-symmetry is maintained.

M is a group IV transition metal of the periodic table, which isillustratively titanium, zirconium or hafnium, preferably zirconium orhafnium.

X and Y are each independently hydrogen, a halogen, a hydrocarbon grouphaving from 1 to 20, preferably from 1 to 10, carbon atoms, an alkoxygroup having from 1 to 20, preferably from 1 to 10, carbon atoms, analkylamido group, a phosphorus-containing hydrocarbon group having from1 to 20, preferably from 1 to 12, carbon atoms or a silicon-containinghydrocarbon group having from 1 to 20, preferably from 1 to 12, carbonatoms. X and Y may be the same or different from each other. Among them,a halogen, a hydrocarbon group and an alkylamido group is desirable.

Among the metallocene compounds represented by the general formula (I),dichloro[dimethylsilylene-(cyclopentadienyl)(2,4-dimethyl-4H-1-azulenyl)]hafniumis most particularly desirable for the production of a propylene polymermain chain having characteristics of the invention, anddichloro[dimethylgermilene(cyclopentadienyl)(2,4-dimethyl-4H-1-azulenyl)]hafniumanddichloro[dimethylsilylene(2-methyl-1-indenyl)(2,4-dimethyl-4H-1-azulenyl)]hafniumare also suitable catalysts.

In this connection, regarding the [A] component metallocene compound, amixture of two or more compounds having different structures may beused, or two or more compounds may be used in combination. In addition,a known solid catalyst containing titanium trichloride as the maincomponent or a carrier-supporting type catalyst containing magnesium,titanium and halogen as essential components can be used as a auxiliarycatalyst. Also, the [A] component may be used by again adding it at thetime of the completion of the first stage polymerization or beforecommencement of the second stage polymerization.

As the co-catalyst ([B] component) to be used in the invention, one ormore substances are used as essential components which are selected fromthe group consisting of (1) an organic aluminumoxy compound, (2) anionic compound capable of exchanging the [A] component into cation byreacting with the transition metal of [A] component, (3) a Lewis acidand (4) an ion exchanging layer compound excluding silicate or aninorganic silicate.

As the organic aluminumoxy compound of (1), the compounds represented bythe following general formulae (II), (III) and (IV) can be cited asillustrative examples.

In these general formulae, R⁴ represents hydrogen atom or a hydrocarbonresidue, preferably a hydrocarbon residue having from 1 to 10, morepreferably from 1 to 6, carbon atoms. Also, two or more of R⁴ may be thesame or different from one another. Also, p is an integer of from 0 to40, preferably from 2 to 30.

The compounds represented by the general formulae (II) and (III) are acompound called aluminoxane which is obtained by the reaction of onespecies of trialkylaluminum or two or more species of trialkylaluminumwith water. Its illustrative examples include (a) methylaluminoxane,ethylaluminoxane, propylaluminoxane, butylaluminoxane, andisobutylaluminoxane obtained from one trialkylaluminum species and waterand (b) methylethylaluminoxane, methylbutylaluminoxane andmethylisobutylaluminoxane obtained from two trialkylaluminum species andwater. Preferred among them are methylaluminoxane andmethylisobutylaluminoxane. It is possible to use the aluminoxane incombination of two or more species. Also, the aluminoxane can beprepared under various known conditions.

The compound represented by the general formula (IV) can be obtained bya 10:1 to 1:1 (molar ratio) reaction of one species of trialkylaluminumor two or more species of trialkylaluminum with an alkylboronic acidrepresented by the following general formula (V). In the general formula(V), R⁵ represents a hydrocarbon residue having from 1 to 10, preferablyfrom 1 to 6, carbon atoms or a halogenated hydrocarbon group.R⁵—B(OH)₂  (V)

Its illustrative examples include the following reaction products,namely, (a) a 2:1 reaction product of trimethylaluminum withmethylboronic acid, (b) a 2:1 reaction product of triisobutylaluminumwith methylboronic acid, (c) a 1:1:1 reaction product oftrimethylaluminum and triisobutylaluminum with methylboronic acid, (d) a2:1 reaction product of trimethylaluminum with ethylboronic acid and (e)a 2:1 reaction product of triethylaluminum with butylboronic acid.

Also, as the (2) ionic compound capable of exchanging the [A] componentinto cation by reacting with the transition metal of [A] component, thecompounds represented by a general formula (VI) can be exemplified.[K]^(n+)[Z]^(n−)  [VI]

In the general formula (VI), K is a cationic component and its examplesinclude carbonium cation, tropylim cation, ammonium cation, oxoniumcation, sulfonium cation and phosphonium cation. Also included arecation of a metal and cation of an organic metal, which by themselvesare apt to be reduced.

Illustrative examples of the cation include triphenylcarbonium,diphenylcarbonium, cycloheptatrienium, indenium, triethylammonium,tripropylammonium, tributylammonium, N,N-dimethylanilinium,dipropylammonium, dicyclohexylammonium, triphenylphosphonium,trimethylphosphonium, tris(dimethylphenyl)phosphonium,tris(methylphenyl)phosphonium, triphenylsulfonium, triphenyloxonium,triethylbxonium, pyrylium, silver ion, gold ion, platinum ion, copperion, palladium ion, mercury ion and ferrocenium ion.

In the general formula (VI), Z is an anion component which is acomponent that becomes counter-anion for a cation species converted fromthe [A] component transition metal (generally a non-coordinationcomponent). As Z, an organic boron compound anion, an organic aluminumcompound anion, an organic gallium compound anion, an organic arseniccompound anion and an organic antimony compound anion can beexemplified, and the following compounds can be cited as illustrativeexamples. That is, (a) tetraphenylboron,tetrakis(3,4,5-trifluorophenyl)boron,tetrakis{3,5-bis(trifluoromethyl)phenyl}boron,tetrakis-{3,5-di(t-butyl)phenyl}boron andtetrakis(pentafluorophenyl)boron and (b) tetraphenylaluminum,tetrakis(3,4,5-trifluorophenyl)aluminum,tetrakis{3,5-bis(trifluoromethyl)phenyl}aluminum,tetrakis{3,5-di(t-butyl)-phenyl}aluminum andtetrakis(pentafluorophenyl)aluminum can be exemplified.

Other illustrative examples include (c) tetraphenylgallium,tetrakis(3,4,5-trifluorophenyl)gallium,tetrakis{3,5-bis(trifluoromethyl)phenyl}gallium,tetrakis-{3,5-di(t-butyl)phenyl}gallium andtetrakis-(pentafluorophenyl)gallium, (d) tetraphenylphosphorus andtetrakis(pentafluorophenyl)phosphorus, (e) tetraphenyl-arsenic andtetrakis(pentafluorophenyl)arsenic, (f) tetraphenylantimony andtetrakis(pentafluorophenyl)-antimony and (g) decaborate, undecaborate,carbadodecaborate and decachlorodecaborate.

Also, as the (3) Lewis acid, particularly a Lewis acid capable ofconverting the [A] component transition metal into cation, variousorganic boron compounds, metal halide compounds and solid acids can beexemplified, and the following compounds can be cited as theirillustrative examples. That is, (a) organic boron compounds such astriphenylboron, tris(3,5-difluorophenyl)boron andtris(pentafluorophenyl)boron, (b) metal halide compounds such asaluminum chloride, aluminum bromide, aluminum iodide, magnesiumchloride, magnesium bromide, magnesium iodide magnesium chloridebromide, magnesium chloride iodide, magnesium bromide iodide, magnesiumchloride hydride, magnesium chloride hydroxide, magnesium bromidehydroxide, magnesium chloride alkoxide and magnesium bromide alkoxideand (c) solid acids such as alumina and silica-alumina can beexemplified.

The (4) ion exchanging layer compound excluding silicate is a compoundwhich forms a crystal structure in which planes constituted by a bondsuch as ionic bond are mutually piled up in parallel through a weakbinding power, wherein the contained ion can be exchanged.

As the ion exchanging layer compound excluding silicate, ioniccrystalline compounds having layer crystal structures such as ofhexagonal closest packing type, antimony type, CdCl₂ type and CdI₂ typecan be exemplified.

Illustratively, crystalline acidic salts of polyvalent metals, such asα-Zr(HAsO₄)₂.H₂O, α-Zr(HPO₄)₂, α-Zr(KPO₄)₂.3H₂O, α-Ti(HPO₄)₂,α-Ti(HAsO₄)₂.H₂O, α-Sn(HPO₄)₂.H₂O, γ-Zr (HPO₄)₂, γ-Ti(HPO₄)₂ and γ-Ti(NH₄PO₄)₂.H₂O, can be cited.

Also, as the inorganic silicate, clay, clay mineral, zeolite anddiatomaceous earth can be exemplified. These may be synthesized productsor naturally produced minerals.

Illustrative examples of the clay and clay mineral include allophanegroups such as allophane, kaolin groups such as dickite, nacrite,kaolinite and anorthite, halloysite groups such as metahalloysite andhalloysite, serpentine groups such as chrysotile, lizardite andantigorite, smectites such as montmorillonite, zauconite, beidellite,nontronite, saponite and hectorite, vermiculite minerals such asvermiculite, mica minerals such as illite, sericite and glauconite,attapulgite, sepiolite, paygorskite, bentonite, kibushi clay, gairomeclay, hisingerite, pyrophyllite and chlorite groups. These may formmixed layers.

As the artificially synthesized products, synthetic mica, synthetichectorite, synthetic saponite and synthetic taeniolite can beexemplified.

Preferred among these illustrative examples are kaolin groups such asdickite, nacrite, kaolinite and anorthite, halloysite groups such asmetahalloysite and halloysite, serpentine groups such as chrysotile,lizaldite and antigorite, smectites such as montmorillonite, zauconite,beidellite, nontronite, saponite and hectorite, vermiculite mineralssuch as vermiculite, mica minerals such as illite, sericite andglauconite, synthetic mica, synthetic hectorite, synthetic saponite andsynthetic taeniolite, and particularly preferred are smectites such asmontmorillonite, zauconite, beidellite, nontronite, saponite andhectorite, vermiculite minerals such as vermiculite, and synthetic mica,synthetic hectorite, synthetic saponite and synthetic taeniolite.

These ion exchanging layer compounds excluding silicate or inorganicsilicates may be used as such, but it is desirable to carry out atreatment with an acid such as hydrochloric acid, nitric acid orsulfuric acid and/or a treatment with a salt such as LiCl, NaCl, KCl,CaCl₂, MgCl₂, Li₂SO₄, MgSO₄, ZnSO₄, Ti(SO₄)₂, Zr(SO₄)₂ or Al₂(SO₄)₃. Inthis case, the treatment may be carried out by mixing corresponding acidand base to form a salt in the reaction system. Also, a shape controlsuch as pulverization or granulation may be carried out, and it isdesirable to carry out granulation for the purpose of obtaining a solidcatalyst component having excellent particle fluidity. In addition, thiscomponent is used generally after dehydration drying. As an essentialcomponent of these [B] components, it is desirable to use (4) an ionexchanging layer compound excluding silicate or an inorganic silicate inview of catalyst performance such as polymerization activity.

In producing the propylene polymer main chain of the invention, anorganic aluminum compound may be used as an optional component [C], inaddition to the co-catalyst [B] component. The organic aluminum compoundis a compound represented by a general formula AlR¹ _(m)Z_(s-m) (whereinR¹ is a hydrocarbon group having from 1 to 20 carbon atoms, Z ishydrogen, a halogen, an alkoxy group or an aryloxy group, and m is anumber of 0<m≦3). Illustratively, it is a trialkylaluminum such astrimethylalminum, triethylaluminum, tripropylaluminum ortriisobutylaluminum, a halogen- or alkoxy-containing alkylaluminum suchas diethylalminum monochloride or diethylalminum ethoxide, or ahydrogen-containing organic aluminum compound such as diethylaluminumhydride or diisobutylaluminum hydride. In addition to this, analuminoxane such as methylaluminoxane can also be used. Particularlypreferred among them is a trialkylaluminum. These optional componentsmay be used in combination of two or more. Also, the optional component[C] may be again added, e.g., after commencement of the polymerization.

The catalyst for propylene polymerization use is obtained through thecontact of the [A] component, [B] component and [C] component, but thecontacting method is not particularly limited. This contact may becarried out not only at the time of the catalyst preparation but also atthe time of the preliminary polymerization or polymerization ofpropylene.

The propylene polymer and solid of an inorganic oxide such as silica oralumina may be allowed to coexist or contact at the time of the contactof respective catalyst component or after the contact.

The contact may be carried out in an inert gas such as nitrogen or in aninert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane,toluene or xylene. It is desirable to use these solvents after applyingthem to an operation for removing poisoning substances such as water andsulfur compounds. It is desirable to carry out the contact at atemperature of from −20° C. to boiling point of the solvent to be used,particularly from room temperature to boiling point of the solvent to beused.

Amount of each of the catalyst components is not particularly limited,but when an ion exchanging layer compound excluding silicate or aninorganic silicate is used as the [B] component, the [A] component isfrom 0.0001 to 10 mmol, preferably from 0.001 to 5 mmol, and the [C]component is from 0 to 10,000 mmol, preferably from 0.01 to 100 mmol,based on 1 g of the [B] component. Also; in view, e.g., ofpolymerization activity, it is desirable to control atomic ratio of thetransition metal in the [A] component and aluminum in the [C] componentat a level of from 1:0 to 1,000,000, preferably from 1:0.1 to 100,000.

The catalyst obtained in this manner may be used after washing with aninert hydrocarbon solvent such as n-pentane, n-hexane, n-heptane,toluene or xylene, or without washing.

In carrying out the washing, the [C] component may be again used incombination as occasion demands. In that case, it is desirable tocontrol the [C] component to be used at such an amount that atomic ratioof aluminum in the [C] component to the transition metal in the [A]component becomes from 1:0 to 10,000.

A product obtained by preliminarily polymerizing propylene and washingit as occasion demands can also be used as the catalyst. Thispreliminary polymerization may be carried out in an inert gas such asnitrogen using an inert hydrocarbon solvent such as pentane, hexane,heptane, toluene or xylene.

The polymerization reaction of propylene is carried out in the presenceor absence of the liquid of an inert hydrocarbon such as propane,n-butane, n-hexane, n-heptane, toluene, xylene, cyclohexane ormethylcyclohexane or liquid of liquefied propylene. Particularly, it isdesirable to carry out the polymerization in the presence of the inerthydrocarbon.

Illustratively, the propylene polymer main chain is produced in thepresence of the [A] component and [B] component or the [A] component,[B] component and [C] component. The polymerization temperature,polymerization pressure and polymerization time are not particularlylimited, but optimum setting can be carried out from the followingranges by taking productivity and process capacity into consideration.That is, the polymerization temperature is selected from the range ofgenerally from 0 to 150° C., preferably from 20 to 100° C., thepolymerization pressure from 0.1 MPa to 100 MPa, preferably from 0.3 MPato 10 MPa, more preferably from 0.5 MPa to 4 MPa, and the polymerizationtime from 0.1 hour to 10 hours, preferably from 0.3 hour to 7 hours,more preferably from 0.5 hour to 6 hours.

According to the invention, it is desirable to control weight averagemolecular weight Mw of the polymer within the range of from 5,000 to200,000 as described above. For this purpose, conventionally knownmethods can be used in controlling molecular weight of the polymer. Thatis, a method in which the molecular weight is controlled by regulatingthe polymerization temperature, a method in which the molecular weightis controlled by regulating the monomer concentration and a method inwhich the molecular weight is controlled by using a chain transfer agentcan be exemplified. When a chain transfer agent is used, hydrogen isdesirable.

Also, regarding the propylene polymer main chain of the inventionproduced by controlling stereoregularity of the propylene unit chainregion comprising a head to tail bond, it is desirable that, when peaksoriginated from the carbon atom of methyl group in a propylene unitchain region comprising a head to tail bond are measured by ¹³C-NMR asdescribed in the foregoing and when chemical shift of the peak top of apeak assigned for a pentad represented by mmmm is defined as 21.8 ppm,ratio of area S₁ of a peak having a peak top of 21.8 ppm to the totalarea S of peaks found at from 19.8 ppm to 22.2 ppm (S₁/S) is 10% or moreand 60% or less, and when area of a peak having a peak top of 21.5 to21.7 ppm (mmmr) is defined as S₂, 4+2S₁/S₂>5.

Method for controlling the stereoregularity related to suchcharacteristics of the propylene polymer main chain is not particularlylimited, but generally, a method in which it is controlled by thestructure of catalyst and a method in which it is controlled byregulating polymerization condition can be exemplified. When thestereoregularity is controlled by regulating polymerization conditions,a propylene polymer main chain having desired stereoregularity can beobtained by regulating polymerization temperature and monomerconcentration and, if necessary, by jointly regulating the catalyststructure.

The propylene polymer main chain to be used in the invention can bedissolved in a solvent. Illustrative examples of the solvent includearomatic hydrocarbons such as benzene, toluene and xylene; aliphatichydrocarbons such as n-pentane, n-hexane, n-heptane, n-octane andn-decane; alicyclic aliphatic hydrocarbons such as cyclohexane,methylcyclohexane and dimethylcyclohexane; halogenated hydrocarbons suchas methylene chloride, carbon tetrachloride, trichloroethylene,perchloroethylene, chlorobenzene and o-dichlorobenzene; esters such asn-ethyl acetate and n-butyl acetate; ketones such as methyl isobutylketone and cyclohexanone; and polar solvents such as tetrahydrofuran anddimethyl sulfoxide; of which aromatic hydrocarbons or halogenatedhydrocarbons are preferred, and toluene, xylene and chlorobenzene areparticularly preferred.

Its solubility is markedly high in comparison with conventional modifiedisotactic polypropylene having high stereoregularity, and when dissolvedin toluene at room temperature (25° C.) to a concentration of 10% byweight, the insoluble matter is 1% by weight or less of the total amountof the polymer. The content is preferably 0.1% by weight and practicallyno insoluble matter is more preferable. In the same manner, whendissolved in boiling heptane (98° C.) to a concentration of 10% byweight, the insoluble matter is 1% by weight or less of the total amountof the polymer.

As the measuring method, a method is used in which a solution dissolvedat a predetermined temperature in a predetermined concentration isfiltered at around the temperature (filtration at the time of heatingwhen the temperature is high), and the weight of insoluble matter ismeasured by drying the filter paper or stainless-steel screen usedtherein.

The method for producing a propylene polymer which has a main chaincomprising the propylene polymer of the invention and a side chaincontaining a carboxylic acid group, an acid anhydride group or acarboxylic acid ester group is not particularly limited, but it isgeneral to use a method in which the polymer is obtained bygraft-polymerizing a polymerizable monomer containing a carboxylic acidor a derivative thereof to the propylene polymer main chain. As thepolymerizable monomer containing a carboxylic acid or a derivativethereof to be subjected to the graft polymerization, (meth)acrylic acidand a derivative thereof and a monoolefin dicarboxylic acid, ananhydride thereof and monoesters thereof can be exemplified, and atleast one species selected therefrom is used. Illustrative examples ofthe (meth)acrylic acid and a derivative thereof include (meth)acrylicacid; a (meth)acrylic acid ester monomer having an alkyl group of from 1to 12 carbon atoms, such as methyl(meth)acrylate, ethyl(meth)acrylate,n-propyl(meth)acrylate, isopropyl(meth)acrylate, n-butyl(meth)acrylate,isobutyl(meth)acrylate, t-butyl(meth)acrylate, pentyl(meth)acrylate,hexyl(meth)acrylate, cyclohexyl(meth)acrylate, octyl(meth)acrylate,2-ethylhexyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate ordodecyl(meth)acrylate; and a (meth)acrylic acid ester monomer having anaryl or arylalkyl group of from 6 to 12 carbon atoms, such asphenyl(meth)acrylate, tolyl(meth)acrylate or benzyl(meth)acrylate.

Other examples of the (meth)acrylic acid derivative include a heteroatom-containing (meth)acrylic acid ester monomer having an alkyl groupof from 1 to 20 carbon atoms, such as hydroxyethyl(meth)acrylate,dimethylaminoethyl(meth)acrylate, diethylaminoethyl(meth)acrylate,2-aminoethyl(meth)acrylate, 2-methoxyethyl(meth)acrylate,3-methoxypropyl(meth)acrylate, glycidyl(meth)acrylate or (meth)acrylicacid ethylene oxide addition product; a fluorine atom-containing(meth)acrylic acid ester monomer having an alkyl group of from 1 to 20carbon atoms, such as trifluoromethylmethyl(meth)acrylate,2-trifluoromethylethyl(meth)acrylate or2-perfluoroethylethyl(meth)acrylate; and a (meth)acrylamide monomer suchas (meth)acrylamide or (meth)acryldimethylamide.

A monoolefin dicarboxylic acid and an anhydride thereof and a monoalkylester of a monoolefin dicarboxylic acid can also be exemplified, andexamples of the monoolefin dicarboxylic acid include maleic acid,chloromaleic acid, citraconic acid, itaconic acid, glutaconic acid,3-methyl-2-pentene diacid, 2-methyl-2-pentene diacid and 2-hexenediacid. Also, as the monoolefin dicarboxylic acid monoalkyl ester, analkyl alcohol having from 1 to 12 carbon atoms and its monoester with adicarboxylic acid can be exemplified, and illustrative examples of thealkyl alcohol include methyl alcohol, ethyl alcohol, propyl alcohol,butyl alcohol, pentyl alcohol, octyl alcohol and cyclohexyl alcohol.

When a coating layer is formed using the graft modified propylenepolymer of the invention, those which have high solubility parameter aredesirable as the polymerizable monomers containing these carboxylicacids or derivatives thereof to be grafted from the viewpoint of theadhesiveness between the coating layer and a paint, that is, unsaturatedcarboxylic acid derivative components comprising an unsaturatedcarboxylic acid having from 3 to 10 carbon atoms, an acid anhydridethereof and an ester thereof is desirable, and maleic anhydride isparticularly desirable.

Among graft modified propylene polymers of the invention, a modifiedpolymer having a monoolefin dicarboxylic acid monoalkyl ester as thegraft copolymerization unit can be obtained, e.g., by a method in whicha monoolefin dicarboxylic acid monoalkyl ester is graft-copolymerized tothe propylene polymer main chain; or a method in which a monoolefindicarboxylic acid or an acid anhydride thereof is graft-copolymerized tothe propylene polymer main chain and then one of the carboxylic acidgroups is esterified by an alkyl alcohol.

It is desirable to carry out the graft copolymerization in such a mannerthat the grafted amount of at least one graft copolymerization unitselected from the polymerizable monomers containing a carboxylic acidgroup or a derivative thereof in the graft modified propylene polymer,namely its content (graft ratio) in the propylene polymer, becomes from0.01 to 25% by weight, preferably from 0.1 to 15% by weight. A propylenepolymer having the graft ratio within this range is preferable from theviewpoint that, when this is coated as a primer on a molded product, acoating layer having high adhesiveness of a paint is obtained,adhesiveness between the coating layer and molded product becomes alsogood and the appearance becomes good.

In addition, as will be described later, the propylene polymer of theinvention shows superior solubility, namely, when it is dissolved intoluene to a concentration of 10% by weight at 25° C., the insolublematter is 1% by weight or less based on the total polymer, and inaddition to this, it also has high adhesiveness to a polypropylenemolded body to be used as the base material. That is, the propylenepolymer of the invention is excellent in the adhesiveness to apolypropylene molded body, and its adhesiveness measured by an adhesiontest (cross-cut tape method) is 50/100 or more, preferably 80/100 ormore, and more preferably 100/100. Particularly, as a propylene polymerhaving such excellent characteristics, those in which a polymerizablemonomer containing a carboxylic acid group or a derivative thereof isgraft-copolymerized to the propylene polymer main chain can beexemplified.

According to the invention, adhesiveness of propylene polymers ismeasured by the following adhesion test.

Adhesion Test

(A) The adhesion test is carried out in accordance with the cross-cuttape method described in JIS K5400 8.5.2.

(1) Summary

Cuts penetrating the coating layer of a test piece and reaching the basematerial face are applied in a cross-cut shape, an adhesive tape isadhered on the cross-cuts, and adhered condition of the coating layerafter peeling is observed with the naked eye.

(2) Tools and Materials

(a) Cutter knife: Defined by JIS K5400 7.2(2) (e).

(b) Cutter guide: Defined by JIS K5400 8.5.1(2) (b).

(c) Cellophane adhesive tape: A cellophane adhesive tape defined by JISZ1522, having a width of 18 mm or 24 mm and an adhesive strength of 2.94N/10 mm or more.

(d) Test plate: A polypropylene test piece (150 mm×70 mm×3 mm).

(e) Eraser: Defined by JIS S6050.

(3) Preparation of Test Piece

A sample is coated and dried on one side of a test piece by a methoddefined by JIS K5400 3.3 for a product standard of samples, and thenallowed to stand for 24 hours under the standard condition.

(4) Operation

In accordance with JIS K5400 8.5.2. (4).

(5) Evaluation

The evaluation is carried out as follows.

(a) Conditions of the cross-cut shaped cuts applied to the coating layerof test piece are observed, and the number of un-peeled cross-cuts among100 cross-cuts is counted and expressed as “the number of residualcross-cuts/100” to be used as the adhesiveness.

A crystalline polypropylene is used as the polypropylene base materialto be used in the adhesion test of the invention. Examples of thecrystalline polypropylene include a propylene homopolymer, and/or apropylene-ethylene block copolymer having a propylene homopolymer moietyand a propylene-ethylene copolymer moiety. Among them, it is desirableto use a propylene homopolymer having an MFR (230° C., 21.18 N loading)of from 5 to 30 (g/10 min).

Various known methods can be exemplified as the method forgraft-copolymerizing a polymerizable monomer such as a monoolefindicarboxylic acid, an acid anhydride thereof or a monoolefindicarboxylic acid monoalkyl ester to the propylene polymer main chain.For example, a method in which the graft copolymerization reaction iscarried out by dissolving the propylene polymer main chain in an organicsolvent, adding the polymerizable monomer to be grafted and a radicalpolymerization initiator and then stirring the mixture under heating; amethod in which the graft copolymerization is effected by melting thepropylene polymer main chain with heating, adding the polymerizablemonomer to be grafted and a radical polymerization initiator to the meltand then stirring the mixture; a method in which the graftcopolymerization is effected by feeding respective components into anextruder and heat-kneading them; and a method in which the graftcopolymerization is effected by impregnating powder of the propylenepolymer with a solution prepared by dissolving the polymerizable monomerto be grafted and a radical polymerization initiator in an organicsolvent, and then heating at a temperature by which the powder is notdissolved can be cited.

In this case, the using ratio of radical polymerizationinitiator/polymerizable monomer to be grafted is within the range ofgenerally from 1/100 to 3/5, preferably from 1/20 to 1/2, as a molarratio.

The reaction temperature is 50° C. or more, particularly desirablywithin the range of from 80 to 200° C., and the reaction time isapproximately from 2 to 10 hours.

The radical polymerization initiator to be used in the graftcopolymerization can be used by optionally selecting from generalradical initiators such as an organic peroxide and an azonitrile.Examples of the organic peroxide include diisopropyl peroxide,di(t-butyl) peroxide, t-butyl hydroperoxide, benzoyl peroxide, dicumylperoxide, cumyl hydroperoxide, dilauroyl peroxide, dibenzoyl peroxide,methyl ethyl ketone peroxide, cyclohexanone peroxide, cumenehydroperoxide, diisopropyl peroxycarbonate and dicyclohexylperoxycarbonate. Examples of the azonitrile include azobisbutyronitrileand azobisisopropylnitrile. Among them, benzoyl peroxide and dicumylperoxide are preferred.

When the graft copolymerization reaction is carried out using an organicsolvent, illustrative examples of the organic solvent include aromatichydrocarbons such as benzene, toluene and xylene; aliphatic hydrocarbonssuch as hexane, heptane, octane and decane; and halogenated hydrocarbonssuch as trichloroethylene, perchloroethylene, chlorobenzene ando-dichlorobenzene, of which an aromatic hydrocarbon or a halogenatedhydrocarbon is preferred, and toluene, xylene and chlorobenzene areparticularly preferred.

The propylene polymer of the invention can also be dissolved in asimilar solvent in which the propylene polymer main chain can bedissolved. Its solubility is markedly high in comparison with generalisotactic polypropylene polymer having high stereoregularity, and whendissolved in toluene at 25° C. to a concentration of 10% by weight, theinsoluble matter is 1% by weight or less of the total amount of thepolymer. The content is preferably 0.1% by weight or less andpractically no insoluble matter is more preferable. Also, since thepropylene polymer of the invention is highly soluble in a solventparticularly having a solubility parameter of 11 (cal/cm³)^(1/2) orless, a composition prepared by dissolving 1 weight part or more of thegraft modified propylene polymer in a solvent having a solubilityparameter of 11 (cal/cm³)^(1/2) or less can be used as an adhesivecomposition.

Illustrative examples of the solvent having a solubility parameter of 11(cal/cm³)^(1/2) or less include aromatic hydrocarbons such as benzene,toluene and xylene; aliphatic hydrocarbons such as n-pentane, n-hexane,n-heptane, n-octane and n-decane; alicyclic aliphatic hydrocarbons suchas cyclohexane, methylcyclohexane and dimethylcyclohexane; halogenatedhydrocarbons such as methylene chloride, chloroform, carbontetrachloride, trichloroethylene, perchloroethylene, chlorobenzene ando-dichlorobenzene; esters such as n-methyl acetate, n-ethyl acetate andn-butyl acetate; ketones such as methyl isobutyl ketone andcyclohexanone; and ethers such as tetrahydrofuran; of which aromatichydrocarbons or halogenated hydrocarbons are preferred, and toluene,xylene and chlorobenzene are particularly preferred.

Also, since the propylene polymer of the invention has suitablestereoregularity distribution of methyl group in the polymer main chainsimilar to the case of the propylene polymer main chain, it has acharacteristic in that its crystallinity is also relatively low and ithas good solubility in a solvent. Illustratively, it is a characteristicthat substantially all components are eluted at 60° C. or less when thepolymer is subjected to temperature rising elution fractionation witho-dichlorobenzene. Since the components eluted at a temperature ofhigher than 60° C. are components having markedly high crystallinity, incase that the polymer contains such components, it is apt to causeinconveniences when the polymer is dissolved in a solvent, such asformation of insoluble matter from such components having highcrystallinity and generation of gelation. Since substantially allcomponents of the propylene polymer of the invention are eluted at 60°C. or less, such inconveniences can be avoided, but it is desirable thatsubstantially all components are eluted at preferably 50° C. or less,more preferably at 40° C. or less.

Since the propylene polymer of the invention is soluble in a solvent, itcan be coated on a compact (base material) of an olefinic polymer havingcrystallinity. Examples of the olefinic polymer as the base materialinclude olefinic polymers such as low density polyethylene, linear lowdensity polyethylene, high density polyethylene, polypropylene,poly-4-methyl-1-pentene, poly-1-butene and polystyrene, and olefiniccopolymers such as an ethylene-propylene copolymer, an ethylene-butenecopolymer and a propylene-butene copolymer. Among these olefiniccopolymers, a propylene copolymer is desirably used. Also, it can beused in moldings comprising polypropylene and synthetic rubber andmoldings comprising a polyamide resin, an unsaturated polyester resin, apolybutylene terephthalate resin and a polycarbonate resin, e.g.,moldings of automobile bumpers, and also in the surface finishing ofsteel sheets and steel sheet for electrodeposition. In addition, byunder-coating it on a surface coated with a paint, primer or adhesivecontaining a polyurethane resin, a fatty acid modified polyester resin,an oil-free polyester resin, a melamine resin or epoxy resin as the maincomponent, it can improve adhesive property of the paint and the otherson the surface and also can be used in forming a coating layer havingexcellent properties such as brightness and low temperature impact.

Since the coating layer formed when the propylene polymer of theinvention is coated on a base material comprising an olefinic polymershows good adhesiveness to the base material as described in theforegoing, the propylene polymer of the invention can be used as anadhesive resin for olefinic polymers. In this connection, in order toobtain good adhesiveness for the olefinic polymer base material, it isdesirable to carry out heating after the coating. Though the heatingtemperature is not particularly limited, it is preferably from 50 to150° C., more preferably from 60 to 130° C., when actual use is takeninto consideration. The coating method is not particularly limited too,and conventionally known methods such as spray coating, roller coatingand brush coating can be used.

A paint can be coated on the surface of moldings having coating layersformed by coating the propylene polymer of the invention, by a methodsuch as electrostatic coating, spray painting or brush coating.

Coating of a paint may be carried out by a method in which finishcoating is carried out after under coating. After coating of a paint,moldings having desired coating layer on the surface can be obtained bycuring the coating layer in accordance with a usual method for heatingby electric heat, infrared ray or high frequency wave. The method forcuring coating layer is optionally selected depending, e.g., on thematerial and shape of the moldings and properties of the paint to beused.

The composition prepared by dissolving the propylene polymer of theinvention in a solvent can be used, e.g., as a primer for improvingcoating performance such as adhesive property of a paint on the surface,water resistance and gasoline resistance of moldings, by coating it onthe surface of moldings comprising an α-olefin copolymer and otherpolymers as the main components. Also, making use of its excellentcharacteristics in terms of adhesive property, peel strength and waterresistance, it can be used in a broad range of applications in additionto the use as a primer for moldings, and it is needless to say that itcan be used in applications such as additive agents in adhesives andpaints and ink binders.

Examples of the illustrative applications include a primer forautomobile exterior (bumper) use, an adhesive for construction materialand decorative sheet use, an adhesive for automobile parts, an adhesivefor packing material use, a paint additive agent for automobile interioruse and an ink binder for gravure ink use.

In addition, the composition of the invention may further containvarious types of stabilizers such as an antioxidant, a weatherstabilizer and a heat stabilizer, colorants such as titanium oxide andan organic pigment, and conductivity providing agents such as carbonblack and ferrite.

Also, regarding the moldings to which the composition of the inventionis to be applied, various polymers or resins described in the foregoingmay be formed by any one of known forming methods such as injectionmolding, compression molding, blow molding, extrusion molding androtational molding.

In coating a composition containing the propylene polymer of theinvention on moldings, a coating layer having particularly good adhesiveproperty can be formed also in case that the moldings are formulatedwith inorganic fillers and pigments such as talc, zinc oxide, glassfiber, titanium white and magnesium sulfate.

In addition, the moldings on which the propylene polymer of theinvention is coated may further contain various components such as astabilizer and an ultraviolet absorber.

Examples of the stabilizer to be preferably used in the composition ofthe invention include phenol base stabilizers such as2,6-di-t-butyl-4-methylphenol,tetrakis[methylene(3,5-di-4-hydroxyhydrocinnamate)]methane,metaoctadecyl-3-(4′-hydroxy-3,5-di-t-butyl-phenyl)propionate,2,2′-methylenebis(4-methyl-6-t-butyl-phenol),4,4′-butylidenebis(3-methyl-6-t-butyl-phenol),2,2-thiobis(4-methyl-6-t-butylphenol),1,3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene and1,3,5-tris(2-methyl-4-hydroxy-5-t-butylphenol)butane; sulfur basestabilizers such as dilauryl thiodipropionate and distearylthiodipropionate; and phosphorus base stabilizers such astridecylphosphite and trinonylphenylphosphite.

Also, examples of the ultraviolet absorber include2-hydroxy-4-octoxybenzophenone, 2-ethylhexyl-2-ciano-3,3-diphenylacrylate and paraoctylphenyl salicylate.

The invention is described further illustratively in the following basedon examples and comparative examples, but the invention is notrestricted by these examples without departing the scope of theinvention.

In this connection, measurement of physical properties and performanceof polymers in the following examples and comparative examples wascarried out in the following manner. Also, in each example, all of thecatalyst preparation steps and polymerization steps were carried outunder an atmosphere of purified nitrogen, and solvents were used bydehydrating with a molecular sieve (MS-4A) and then degassing bybubbling with purified nitrogen.

<Measurement of Physical Properties>

(i) Measurement of Physical Properties of Propylene Polymer Main Chain

(1) Measurement of molecular weight of propylene polymer main chain

Measurement of weight average molecular weight Mw, number averagemolecular weight Mn and molecular weight distribution Mw/Mn by GPC wascarried out using GPC 150CV type manufactured by Waters.o-Dichlorobenzene was used as the solvent, and the measuring temperaturewas set to 135° C. In calculating molecular weight, a commerciallyavailable mono-dispersion polystyrene was used as the standard sample,and molecular weight was calculated by preparing a calibration curveregarding retention time and molecular weight from a viscosity formulaof the polystyrene standard sample and polypropylene.

(2) Measurement of the pentads of propylene unit chain region by ¹³C-NMRspectrum was carried out in the following manner.

A 350 to 500 mg portion of a sample was completely dissolved using about2.2 ml of o-dichlorobenzene in a 10 mm φ NMR sample tube. Next, this washomogenized by adding about 0.2 ml of benzene deuteride as a locksolvent, and then the measurement was carried out at 130° C. by a protoncomplete decoupling method. The measuring conditions were set to a flipangle of 90° and a pulse interval of 5T₁ or more (T₁ is the longestvalue among spin-lattice relaxation times of methyl group). Sincespin-lattice relaxation times of methylene group and methine group inpropylene polymers are shorter than those of methyl group, recovery ofmagnetization of all carbons is 99% or more. In this connection, inorder to improve determination accuracy, it is desirable to use an NMRapparatus of 125 MHz or more as the ¹³C nuclear resonance frequency andcarry out integration of 20 hours or more.

(3) Crystallinity was measured by a wide angle X-ray diffractiometry anddetermined by a multiple peak separation method (symmetric throughtransmission method (2θ/θ=5 to 60°, 0.1°/step)).

(4) Melting point Tm and crystal melting calorie were calculated by thefollowing method using a thermal analysis system TA 2000 manufactured byDu Pont.

After melting a sample (about 5 to 10 mg) at 200° C. for 3 minutes, thetemperature was reduced to 30° C. at a rate of 10° C./min and thenincreased to 200° C. at a rate of 10° C./min, thereby obtaining amelting curve, and the peak top temperature of the main endothermic peakat the final temperature rising step was obtained as the melting point.

(5) Temperature rising elution fractionation by o-dichlorobenzene wascarried out using CFC-T-102L manufactured by Mitsubishi ChemicalCorporation (described as 100% elution temperature, the elutionfractionation was started at 5° C. and measured at 4 to 5° C.intervals).

(6) Solubility test was carried out by the following method.

Each propylene polymer was added to a solvent (heptane or toluene) to aconcentration of 10% by weight, put into a separable flask equipped witha mixing blade and then dissolved by rising the outer temperature to110° C. in the case of heptane or 120° C. in the case of toluene. Afterthe inner temperature became constant, stirring was continued for 2hours. This was allowed to stand for 1 hour just after the boilingtemperature in the case of heptane, or after spontaneous cooling to 30°C. in the case of toluene, and then filtered through stainless-steelscreen No. 400. The residue remained on the screen was regarded asinsoluble matter, and the solution passed through the screen as solublematter, and they were dried at 80° C. for 4 hours under 1 mmHg or lessusing a vacuum dryer. Ratio of the insoluble matter was measured byweighing them.

Evaluation Criteria

-   ◯: insoluble matter 1% or less, X: insoluble matter 1% or more

(7) Non-tackiness was evaluated by a finger touch tackiness test.

◯: excellent non-tackiness, Δ: slightly tacky, X: tacky

(ii) Adhesion Test of Propylene Polymer

(1) Adhesion test was carried out in the same manner as described in theforegoing.

In this connection, preparation conditions of test pieces are shown inthe “Reference Example” which will be described later.

(2) Regarding the water resistance test, a coated material prepared byforming a coating layer on a base material using a propylene polymer orother polymer as a primer, coating and curing a base coat on the coatinglayer and then aging it at room temperature was soaked for 10 days inwarm water kept at 40° C. Thereafter, moisture on the surface was driedand then the test was carried out in the same manner as the adhesiontest.

(3) Regarding the gasohol resistance test, a coated material prepared byforming a coating layer on a base material using a propylene polymer orother polymer as a primer, coating and curing a base coat on the coatinglayer and then aging it at room temperature was soaked in a mixedsolvent of regular gasoline:ethanol=9:1 kept at 20° C., and then theperiod until generation of significant peeling of the coating layer wasmeasured.

<Preparation of Test Piece (Base Material)>

REFERENCE EXAMPLE 1

Mixture Composition

Polypropylene block copolymer (trade name: BC06C, mfd. by JapanPolychem, MFR=60) 60 parts by weight

Ethylene-propylene random copolymer (trade name: EPO7P, mfd. by JSR) 30parts by weight

Talc (trade name: MT7, mfd. by Fuji Talc) 10 parts by weight

As an antioxidant, 0.1 part by weight oftetrakis[methylene-3-(3′,5′-di-t-butyl-4′-hydroxyphenyl)-propionate]methane(mfd. by Ciba Specialty Chemicals, IRGANOX 1010) was added to thismixture and mixed for 5 minutes using Henschel mixer, and then theresulting mixture was subjected to kneading granulation using a twinscrew kneading machine (KCM 50, mfd. by Kobe Steel) at a settingtemperature of 210° C. to obtain a thermoplastic resin composition.Thereafter, using an injection molding machine manufactured by ToshibaMachine (Toshiba IS170) and at a molding temperature of 220° C., thiscomposition was formed into a test piece having a shape of 150 mm×70mm×3 mm.

REFERENCE EXAMPLE 2

Using an injection molding machine manufactured by Toshiba Machine(Toshiba IS170) and at a molding temperature of 220° C., a polypropyleneMA3U manufactured by Japan Polychem (propylene homopolymer, MFR: 15 g/10min (230° C., 21.18 N loading)) was formed into a test piece having ashape of 150 mm×70 mm×3 mm.

PRODUCTION EXAMPLE 1

(1) Synthesis ofdichloro[dimethylsilylene(cyclopentadienyl)(2,4-dimethyl-4H-1-azulenyl)]hafnium

(1)-1 Synthesis of Ligand

2-Methylazulene (4.01 g) was dissolved in tetrahydrofuran (56 ml) andcooled to 0° C. in an ice bath, and then 24.8 ml of methyllithiumdiethyl ether solution (1.14 mol/l) was added dropwise thereto at thesame temperature. After completion of the addition, the ice bath wasremoved and the mixture was stirred for 2 hours. This solution wasslowly added dropwise to dimethylsilyl dichloride (34.0 ml, 0.280 mol)tetrahydrofuran solution (140 ml) which was cooled at 0° C. in an icebath. After completion of the addition, the ice bath was removed, themixture was stirred for 3 hours, and then the solvent and unreacteddimethylsilyl dichloride were evaporated under a reduced pressure. Theresidue was mixed with tetrahydrofuran (80 ml) and cooled to 0° C.,cyclopentadienyl sodium (2.1 mol/l, 26.9 ml, 56.5 mmol) was graduallyadded dropwise thereto, and after completion of the addition, themixture was stirred at room temperature for 12 hours. After completionof the stirring, this was mixed with water and the compound of interestwas extracted with diethyl ether. The extract was dehydrated usingmagnesium sulfate and then dried to obtain unpurified product of theligand of interest. By purifying the crude product by a silica gelcolumn chromatography using n-hexane as the elution solvent, the ligandof interest (6.29 g) was obtained with a yield of 79%.

(1)-2 Synthesis of Complex

The ligand of interest (6.29 g) obtained in (1)-1 was dissolved intetrahydrofuran (100 ml) and cooled to 0° C. in an ice bath. Ann-buthyllithium n-hexane solution (1.56 mol/l, 28.4 ml) was slowly addeddropwise thereto at the same temperature. After completion of theaddition, the ice bath was removed, the mixture was stirred for 3 hours,and then the solvent was evaporated under a reduced pressure. After theevaporation, the thus obtained residue was mixed with toluene (60 ml)and then cooled to −78° C. A toluene (140 ml) suspension of hafniumtetrachloride (7.17 g) cooled to −78° C. was gradually added thereto.Then, after removing the cooling bath, this was stirred overnight. Aftercompletion of the stirring, the reaction solution was filtered using aG3 frit. By further washing the solid on the frit with toluene andconcentrating the filtrate, a brown powder was obtained. The complex ofinterest was extracted from this brown powder with hot n-hexane (180ml×3). After drying the extract, the thus obtained solid was suspendedand washed with n-hexane (20 ml×5) and then dried under a reducedpressure to obtain the intendeddichloro[dimethylsilylene(cyclopentadienyl)-(2,4-dimethyl-4H-1-azulenyl)]hafnium(2.90 g) (yield 25%).

Results of the ¹H-NMR measurement of this compound are as follows.

¹H-NMR (CDCl₃): δ 0.85 (s, 3 H), 0.86 (s, 3H), 1.47 (d, J=7.1 Hz, 3 H),2.25 (s, 3 H), 3.42–3.52 (m, 1 H), 5.42 (dd, J=4.7, 10.1 Hz, 1 H),5.80–5.85 (m, 2 H), 5.90–5.95 (m, 1 H), 6.16–6.20 (m, 2 H), 6.65 (d,J=11.4 H), 6.80–6.85 (m, 1 H), 6.98–7.02 (m, 1 H).

(2) Chemical Treatment of Clay

Deionized water (110 ml), magnesium sulfate.7H₂O (22.2 g) and sulfuricacid (18.2 g) were put into a 1,000 ml round bottom flask and dissolvedunder stirring. A commercially available granulated montmorillonite(Benclay SL, mfd. by Mizusawa Industrial Chemicals, 16.7 g) wasdispersed in this solution, and the suspension was heated to 100° C.spending 2 hours and then stirred at 100° C. for 2 hours. Thereafter,this was cooled to room temperature spending 1 hour, and then the thusobtained slurry was filtered to recover a wet cake. The thus recoveredcake was put into a 1,000 ml round bottom flask and again made into aslurry with deionized water (500 ml) and then filtered. This step wasperformed twice. The finally obtained cake was dried overnight at 110°C. in nitrogen atmosphere to obtain a chemically treated montmorillonite(13.3 g).

(3) Polymerization

The chemically treated montmorillonite (0.44 g) obtained in ProductionExample 1(2) was mixed with a toluene solution of triethylaluminum (0.4mmol/ml, 2.0 ml) and stirred at room temperature for 1 hour. Thissuspension was mixed with toluene (8 ml) and stirred and then thesupernatant was discarded. This step was performed twice, and then theprecipitate was mixed with toluene to obtain a clay slurry (slurryconcentration=99 mg clay/ml).

Triisobutylaluminum manufactured by Tosoh Aqzo (0.114 mmol) was put intoanother flask, mixed with the thus obtained clay slurry (3.8 ml) and atoluene-diluted solution of the complex (6.02 mg, 11.4 μmol) obtained inProduction Example 1(1)-2 and then stirred at room temperature for 10minutes to obtain a catalyst slurry.

Next, toluene (750 ml), triisobutylaluminium (1.9 mmol) and liquidpropylene (180 ml) were put into a 2 liter induction stirring typeautoclave. Whole amount of the above-obtained catalyst slurry was puttherein at room temperature, the mixture was heated to 60° C., and thenthe stirring was continued for 1 hour at the same temperature whilekeeping the total pressure during polymerization at 0.7 MPa. Aftercompletion of the stirring, the polymerization was stopped by purgingunreacted propylene. When total amount of the toluene solution ofpolymer was recovered by opening the autoclave and the solvent and clayresidue were removed, 23.2 g of a propylene polymer was obtained.Results of the analysis of the thus obtained polymer are shown in Table1-1.

PRODUCTION EXAMPLE 2

The same procedure of Production Example 1 was performed, except that17.8 mg (34.2 mmol) of the complex, triisobutylaluminium (0.342 mmol)and the clay slurry (11.4 ml) were used as the materials for clay slurryuse, amounts of toluene (1,100 ml), triisobutylaluminium (0.5 mmol) andliquid propylene (264 ml) were changed, and the temperature duringpolymerization was changed to 80° C., the total pressure to 0.8 MPa andthe polymerization period to 1.83 hours. As a result, 245 g of apropylene polymer was obtained. Results of the analysis of the thusobtained polymer are shown in Table 1-1.

PRODUCTION EXAMPLE 3

The same procedure of Production Example 2 was performed, except thatamounts of toluene (1,350 ml), and liquid propylene (90 ml) werechanged, and the temperature during polymerization was changed to 70°C., the total pressure to 0.31 MPa and the polymerization period to 2hours. As a result, 44 g of a propylene polymer was obtained. Results ofthe analysis of the thus obtained polymer are shown in Table 1-1.

PRODUCTION EXAMPLE 4

The same procedure of Production Example 1 was performed, except thatliquid propylene (182 ml) and triisobutylaluminium (0.5 mmol) were used.As a result, 39.6 g of a propylene polymer was obtained. Results of theanalysis of the thus obtained polymer are shown in Table 1-1.

PRODUCTION EXAMPLE 5

(1) Synthesis of Racemicdichloro{1,1′-dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenyl)-4H-azulenyl]}-hafnium

2-Fluoro-4-bromobiphenyl (6.35 g, 25.3 mmol) was dissolved in a mixedsolvent of diethyl ether (50 ml) and n-hexane (50 ml), and an n-pentanesolution of t-butyllithium (33 ml, 50.6 mmol, 1.54 N) was added dropwisethereto at −78° C. After stirring at −10° C. for 2 hours, this solutionwas mixed with 2-ethylazulene (3.55 g, 22.8 mmol) and stirred at roomtemperature for 2 hours. n-Hexane (30 ml) was added thereto, and thesupernatant was removed by decantation. This step was further performedonce. At 0° C., n-hexane (30 ml) and tetrahydrofuran (40 ml) were addedto the thus obtained yellow precipitate. Next, this was mixed withN-methylimidazole (50 ml) and dimethyldichlorosilane (1.4 ml, 11.4mmol), warmed up to room temperature and then stirred at roomtemperature for 1 hour. Thereafter, this was mixed with dilutedhydrochloric acid and subjected to phase separation, the resultingorganic layer was dried with magnesium sulfate, and then the solvent wasevaporated under a reduced pressure to obtain a crude product ofdimethylsilylenebis(2-ethyl-4-(2-fluoro-4-biphenyl)-1,4-dihydroazulene(8.3 g).

Next, the thus obtained crude product was dissolved in diethyl ether (30ml), an n-hexane solution of n-butyllithium (14.9 ml, 22.8 mmol, 1.53 N)was added dropwise thereto at −70° C., and the mixture was graduallywarmed up and stirred overnight at room temperature. This was mixed withtoluene (200 ml), cooled to −70° C., mixed with hafnium tetrachloride(3.6 g, 11.4 mmol), gradually warmed up and then stirred at roomtemperature for 4 hours. Most of the solvent was evaporated from thethus obtained slurry under a reduced pressure, the residue was mixedwith diethyl ether (50 ml) and then the thus obtained slurry wasfiltered. When this was washed with diethyl ether (5 ml×2), ethanol (15ml×2) and n-hexane (10 ml×2), a racemi-meso mixture ofdichloro{1,1′-dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenyl)-4H-azulenyl]}hafniumwas obtained (4.53 g, yield 42%). As a result of ¹H-NMR analysis of thethus obtained racemi-meso mixture, it was found that this is a mixtureof 76.6% racemic body and 23.4% meso body.

The thus obtained racemi-meso mixture (4.5 g) was suspended indichloromethane (35 ml) and allowed to undergo light irradiation for 1hour using a high pressure mercury lamp (100 W). The solvent wasevaporated under a reduced pressure, and the thus obtained solid wasmixed with toluene (25 ml) and dichloromethane (11 ml) and heated at 60°C. to obtain a uniform solution. Crystals were precipitated whendichloromethane was evaporated under a reduced pressure, and the thusobtained crystals were recovered by filtration, washed twice with hexane(5 ml) and then dried under a reduced pressure to obtain the racemicbody (1.79 g).

(2) Chemical Treatment of Clay

A 55.85 g portion of deionized water, 32.70 g of sulfuric acid and 8.01g of lithium hydroxide were put into a 500 ml round bottom flask andstirred and then 51.65 g of montmorillonite (Mizusawa Smectite, mfd. byMizusawa Industrial Chemicals) was added thereto, and the mixture washeated to carry out the treatment under reflux for 140 minutes. This wasmixed with 300 ml of deionized water and subjected to suctionfiltration, and then the solid matter was dispersed in 600 ml ofdeionized water and subjected to suction filtration. This step wasperformed once again. The residue obtained by filtration was dried at100° C. to obtain an acid- and metal salt-treated montmorillonite.

A 1.05 g portion of the thus obtained acid- and metal salt-treatedmontmorillonite was put into a 100 ml round bottom flask and dried byheating at 200° C. for 2 hours under a reduced pressure. This was mixedwith 4.0 ml of a toluene solution of triethylaluminum (0.5 mmol/ml) inan atmosphere of purified nitrogen, allowed to undergo the reaction atroom temperature for 30 minutes and then washed twice with 30 ml oftoluene, thereby obtaining a toluene slurry containing a chemicallytreated montmorillonite.

(3) Preliminary Polymerization

Toluene was extracted from the toluene slurry obtained in ProductionExample 5(2) (containing 914.2 mg as the solid content) to adjust theresidual toluene content to 1.0 ml. This was mixed with a toluenesolution of triisobutylaluminum (0.5 mmol/ml, 0.5 ml) and then with atoluene solution of the racemic body ofdichloro{1,1′-dimethylsilylenebis[2-ethyl-4-(2-fluoro-4-biphenyl)-4H-azulenyl]}hafniumsynthesized in Production Example 5(1) (3.0 mmol/ml, 9.2 ml) and stirredat room temperature for 1 hour to obtain a catalyst slurry.

In an atmosphere of purified nitrogen, 40 ml of toluene and total amountof the catalyst slurry were put into a 2 liter induction stirring typeautoclave. Under stirring, 11.0 g of propylene was put into theautoclave and preliminary polymerization was carried out at 30° C. for 2hours and then at 50° C. for 0.5 hour. After the preliminarypolymerization, unreacted propylene was purged and replaced by purifiednitrogen twice under a pressure of 0.5 MPa, and then the preliminarypolymerization catalyst was taken out. This product contained 9.7 g of apolymer per 1 g of the chemically treated montmorillonite component.

(4) Polymerization

The atmosphere in a 2 liter induction stirring type autoclave equippedwith an anchor type mixing blade was replaced by purified nitrogen, and750 g of liquid propylene was put into the vessel at 25° C. A toluenesolution of triisobutylaluminum (0.1 mmol/ml, 5.0 ml) was put into thevessel under pressure at the same temperature and then the temperaturewas increased to 70° C. Hydrogen was added to a gas phase hydrogenconcentration of 0.2 mol % and then 30.0 mg of the preliminarypolymerization catalyst obtained in (3) was added at 70° C. to startpolymerization. One hour after, the polymerization was completed bypurging unreacted propylene. Amount of the thus obtained propylenepolymer was 384 g.

Results of the analysis of the thus obtained polymer are shown in Table1-1.

In this connection, the peak originated from the carbon atom of methylgroup of a propylene unit chain region comprising head to tail bond,measured by ¹³C-NMR, was [mmmm]>99.9 (%), and peaks originated fromother pentads were hardly found.

PRODUCTION EXAMPLE 6

A 500 ml induction stirring type micro-autoclave was charged with anisotactic polypropylene having high stereospecificity (31.1 g), heptane(180 ml) and Pd/C (mfd. by Sigma-Aldrich Corporation, 10 wt % Pd/C)(7.87 g), and then the system was closed to carry out nitrogensubstitution. Thereafter, 8.0 MPa of hydrogen was introduced,temperature was raised to 275° C. and then the stirring was continuedfor 6 hours. After cooling, the reaction was stopped by purginghydrogen. When total volume of the heptane solution of polymer wasrecovered by opening the autoclave and the solvent and Pd/C residue wereremoved, 30.6 g of a propylene polymer was obtained. Results of theanalysis of the thus obtained polymer are shown in Table 1-1.

In this connection, physical properties of the highly stereospecificisotactic polypropylene used herein are as follows.

-   MFR: 15,000-   TM: 154.9-   Mw: 37,000; Mn: 18,000; Mw/Mn: 2.1-   [mmmm]: 98.4%; [mmmr]: 0.0%; [rmrm]: 0.1%; [rrrr]: 0.2%

COMPARATIVE PRODUCTION EXAMPLE 1

Physical properties of Ubetac UT-2115 manufactured by Ube Industrieswere measured in the same manner. The results are also shown in Table1-1.

PRODUCTION EXAMPLE 7

The chemically treated montmorillonite (1.02 g) obtained in ProductionExample 1(2) was mixed with a toluene solution of triethylaluminum (0.45mmol/ml, 4.5 ml) and stirred at room temperature for 1 hour. Thissuspension was mixed with toluene (40 ml) and stirred and then thesupernatant was discarded. This step was performed twice, and then theprecipitate was mixed with toluene to obtain a clay slurry (slurryconcentration=99 mg clay/ml)

Triisobutylaluminum manufactured by Tosoh Aqzo (0.08 mmol) was put intoanother flask, mixed with the thus obtained clay slurry and atoluene-diluted solution of the complex (3.86 mg, 7.45 μmol) obtained inProduction Example 1(1)-2 and then stirred at room temperature for 40minutes to obtain a catalyst slurry.

Next, triisobutylaluminum (1.9 mmol) and whole amount of theabove-obtained catalyst slurry were put into a 2 liter inductionstirring type autoclave. Liquid propylene (1250 ml) was put therein atroom temperature, and then ethylene was put therein to the pressure of0.07 MPa (partial pressure of ethylene). The mixture was heated to 60°C., and then the stirring was continued for 1 hour at the sametemperature. After completion of the stirring, the polymerization wasstopped by purging unreacted propylene. When total amount of the toluenesolution of polymer was recovered by opening the autoclave and thesolvent and clay residue were removed, 144 g of a propylene-ethylenecopolymer was obtained, results of the analysis of the thus obtainedpolymer are shown in table 1-2

PRODUCTION EXAMPLE 8

(1) Chemical Treatment of Clay

Deionized water (72 ml), lithium sulfate.1H₂O (11 g) and sulfuric acid(17 g) were put into a 1,000 ml round bottom flask and dissolved understirring. A commercially available granulated montmorillonite (BenclaySL, mfd. By Mizusawa Industrial Chemicals, 22 g) was dispersed in thissolution, and the suspension was heated to 100° C. spending 0.5 hour andthen stirred at 100° C. for 5 hours. Thereafter, this was cooled to roomtemperature spending 1 hour, and then the thus obtained slurry wasfiltered to recover a wet cake. The thus recovered cake was put into a1000 ml round bottom flask and again made into a slurry with deionizedwater (500 ml) and then filtered. This step was performed twice. Thefinally obtained cake was dried for 1 hour at 200° C. in nitrogenatmosphere to obtain a chemically treated montmorillonite (15.6 g).

(2) Polymerization

The chemically treated montmorillonite (0.25 g) obtained in ProductionExample 8(1) was mixed with a toluene solution of triethylaluminum (0.5mmol/ml, 1.0 ml) and stirred at room temperature for 0.5 hour. Thissuspension was mixed with toluene (10 ml) and stirred and then thesupernatant was discarded. This step was performed twice, and then theprecipitate was mixed with toluene to obtain a clay slurry (slurryconcentration=99 mg clay/ml)

Triisobutylaluminum manufactured by Tosoh Aqzo (0.015 mmol) was put intoanother flask, mixed with the thus obtained clay slurry and atoluene-diluted solution of the complex (3.89 mg, 7.5 μmol) obtained inProduction Example 1(1)-2 and then stirred at room temperature for 10minutes to obtain a catalyst slurry.

Next, triisobutylaluminum (0.13 mmol) and toluene (1100 ml) and wholeamount of the above-obtained catalyst slurry were put into a 2 literinduction stirring type autoclave. Liquid propylene (264 ml) was puttherein at room temperature, and then ethylene was put therein to thepressure of 0.025 MPa (partial pressure of ethylene). The mixture washeated to 80° C., and then the mixture gas of ethylene and hydrogen(ethylene:hydrogen=9:1) was fed at the rate of 0.1 MPa·L/hr andpropylene was fed so as to keep the total pressure in the vessel at 0.85MPa. The stirring was continued for 1 hour at the same temperature.After completion of the stirring, the polymerization was stopped bypurging unreacted ethylene and propylene. When total amount of thetoluene solution of polymer was recovered by opening the autoclave andthe solvent and clay residue were removed, 303 g of a propylene-ethylenecopolymer was obtained. Results of the analysis of the thus obtainedpolymer are shown in Table 1-2.

PRODUCTION EXAMPLE 9

The same procedure of Production Example 8 was performed, except thatethylene gas was used instead of the mixture gas of ethylene andhydrogen, and polymerization time was changed to 1.5 hours. As a result,146 g of a propylene-ethylene copolymer was obtained. Results of theanalysis of thus obtained polymer are shown in Table 1-2.

PRODUCTION EXAMPLE 10

The same procedure of Production Example 8 was performed, except thatthe amount of liquid propylene (160 ml), the temperature (80° C.), thepolymerization time (1.5 hours), the total pressure (0.80 MPa), andethylene partial pressure (0.20 MPa) were changed. As a result, 66 g ofa propylene-ethylene copolymer was obtained. Results of the analysis ofthus obtained polymer are shown in Table 1-2.

COMPARATIVE PRODUCTION EXAMPLE 2

Physical properties of Ubetac UT-2215 manufactured by Ube Industrieswere measured in the same manner. The results are also shown in Table1-2.

COMPARATIVE PRODUCTION EXAMPLE 3

Physical properties of Tafmer S4030 manufactured by Mitsui Chemicalswere measured in the same manner. The results are also shown in Table1-2.

TABLE 1-1 Prod. Prod. Prod. Prod. Prod. Prod. UT- Item Unit Ex. 1 Ex. 2Ex. 3 Ex. 4 Ex. 5 Ex. 6 2115 Primary structure Mw 110,000 66,000 69,000130,000 110,000 41,000 26,000 Mn 31,000 20,000 18,000 41,000 53,00019,000 4,500 Mw/Mn 3.5 3.3 3.8 3.2 2.1 2.2 5.8 S₁/S (%) 41.1 35 29.745.4 >99.9 10.7 43.9 S₃/S (%) 1.5 2.7 2.5 1.3 n.d. 6.5 6.6 S₄/S (%) 4.24.9 6.1 3.8 n.d. 11.5 2.1 4 + 2 S₁/S₂ 9.04 8.27 7.64 9.82 >1000 5.6811.3 Crystallinity (%) 14.8 12.6 10.5 16.4 48 n.d. — Melting point Tm (°C.) n.d. n.d. n.d. n.d. 156 n.d. 152 Crystal melting (J/g) n.d. n.d.n.d. n.d. 157 n.d. 18 calorie 100% Elution temp. (° C.) 55 35 35 65 12025 75 Physical properties Insoluble matter (%) <1 <1 <1 <1 98.3 <1 45.4(10 wt % in boiling heptane) Insoluble matter (%) <1 <1 <1 1.5 96.6 <131.6 (10 wt % in toluene) Non-tackiness ◯ ◯ ◯ ◯ ◯ X Δ In this table,“n.d.” represents “not detected”.

TABLE 1-2 Prod. Prod. Prod. Prod. UT- Item Unit Ex. 7 Ex. 8 Ex. 9 Ex. 102215 S4030 Primary structure Mw 91,000 49,000 60,000 70,000 24,000310,000 Mn 18,000 12,000 13,000 15,000 4,400 57,000 Mw/Mn 5.0 4.1 4.64.7 5.6 5.5 S₁/S (%) 35.7 33.1 33.7 26.6 35 13 4 + 2S₁/S₂ 8.8 7.9 7.87.3 10.0 6.4 [E] (wt %) 0.3 1.1 2.2 8.7 2.6 12.8 Crystallinity (%) 16.315.5 15.2 12.0 18.1 5.7 Melting point Tm (° C.) n.d. n.d. n.d. n.d. 143115.9 Crystal Melting calorie (J/g) n.d. n.d. n.d. n.d. 13 2.3 100%Elution temp. (° C.) 65 55 55 45 105 95 Physical properties Insolublematter (%) <1 <1 <1 <1 42.6 filtration was (10 wt % in heptane)impossible Insoluble matter (%) <1 <1 <1 <1 29.7 filtration was (10 wt %in toluene) impossible Non-tackiness ◯ ◯ ◯ ◯ X ◯

EXAMPLE 1

(1) Maleic Anhydride Modification of Propylene Polymer

A stainless steel pressure reaction vessel equipped with a thermometerand a stirrer was charged with chlorobenzene (80 g), the propylenepolymer obtained in Production Example 1(3) (20 g) and maleic anhydride(4 g), the atmosphere in the vessel was replaced by nitrogen gas, andthen the temperature was elevated to 132° C. After the temperaturereached 132° C., 8 g of dicumyl peroxide (DCPO) chlorobenzene solution(20 wt %) was supplied using a metering pump for 5.5 hours, and then thereaction was carried out by continuing the stirring at the sametemperature for 3 hours. After completion of the reaction, the systemwas cooled to about room temperature, acetone was added and then theprecipitated polymer was collected by filtration. The precipitation withacetone and collection by filtration were repeated, and the finallyobtained polymer was washed with acetone. The polymer obtained afterwashing was dried under a reduced pressure to obtain a modified polymeras a white powder. When infrared absorption spectrum measurement andneutralization titration of this modified polymer were carried out, themaleic anhydride group content was 3.3 wt %.

A 15 g portion of the thus obtained maleic anhydride-modified propylenepolymer was mixed with 135 g of toluene, heated to 100° C. and dissolvedin 1 hour. The thus obtained solution was cooled to about roomtemperature and then passed through #400 stainless-steel screen toprepare 10 wt % solution of the maleic anhydride-modified propylenepolymer.

(2) Evaluation of Physical Properties of Modified Propylene Polymer

A toluene solution of the maleic anhydride-modified propylene polymerobtained in Example 1(1) was spray-coated on each of theinjection-molded test pieces (the surfaces of which were wiped withisopropyl alcohol) prepared in Reference Examples 1 and 2. In this case,the coating amount was set to 3 to 5 g/m². Next, this molded test piecewas allowed to stand at 25° C. for 1 hour and then dried at 80° C. for30 minutes in a safety valve dryer. Next, this dried product was allowedto stand at 25° C. for 1 hour, and then a base coat prepared by blendingan acrylpolyol urethane paint Retan PG•80 III (trade name, mfd. byKansai Paint) with a predetermined amount of a curing agent andadjusting the viscosity to 12 to 13 seconds with a special purposethinner using Ford cup No. 4 was spray-coated on the coating layer to adry coat amount of 50 to 60 g and cured at 100° C. for 30 minutes in thesafety valve dryer. This was further cured by allowing it to stand at25° C. for 10 days. The thus obtained coated product was subjected to aninterlayer adhesion test. Its water resistance test and gasoholresistance test were also carried out. The results are shown in Table2-1.

EXAMPLE 2

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thereaction was carried out at 110° C. using 20 g of the propylene polymersynthesized in Production Example 2, 10 g of maleic anhydride and 7 g ofdicumyl peroxide (DCPO) chlorobenzene solution. (20 wt %). The resultsare shown in Table 2-1.

EXAMPLE 3

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene polymer synthesized in Production Example 2 was used. Theresults are shown in Table 2-1.

EXAMPLE 4

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene polymer synthesized in Production Example 3 was used. Theresults are shown in Table 2-1.

EXAMPLE 5

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene polymer synthesized in Production Example 4 was used. Theresults are shown in Table 2-1.

EXAMPLE 6

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except thatmethacrylic acid (5 g) was added instead of maleic anhydride (4 g) andamount of the dicumyl peroxide (DCPO) chlorobenzene solution (20 wt %)was changed to 2.5 g. The results are shown in Table 2-1.

EXAMPLE 7

The modification treatment and preparation of coated product werecarried out by the same methods as Example 6, and evaluation tests onphysical properties were carried out in the same manner, except that2-hydroxyethyl methacrylate (5 g) was added instead of methacrylic acid(5 g). The results are shown in Table 2-1.

EXAMPLE 8

The modification treatment and preparation of coated product werecarried out by the same methods as Example 6, and evaluation tests onphysical properties were carried out in the same manner, except that2-hydroxyethyl methacrylate (5 g) and styrene (5 g) were added insteadof methacrylic acid (5 g). The results are shown in Table 2-1.

COMPARATIVE EXAMPLE 1

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, except that the propylenepolymer synthesized in Production Example 5 was used. Since the thusobtained modified polypropylene polymer showed poor solubility intoluene and 96% thereof was insoluble matter, the coating evaluationcannot be made.

COMPARATIVE EXAMPLE 2

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene polymer synthesized in Production Example 6 was used. Theresults are shown in Table 2-2.

COMPARATIVE EXAMPLE 3

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except thatUbetac UT-2115 manufactured by Ube Industries (a Ziegler-Natta catalystbased polypropylene) was used. The results are shown in Table 2-2.

COMPARATIVE EXAMPLE 4

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except thatTafmer XR-110T manufactured by Mitsui Chemicals (a propylene-butene-1copolymer, propylene component:butene-1 component=76:24) was used. Theresults are shown in Table 2-2.

COMPARATIVE EXAMPLE 5

The evaluation was carried out in the same manner as in Example 1(2),using CP-343-1 manufactured by Eastman Chemical (a maleicanhydride-modified chlorinated polypropylene) as the modified polymer.The results are shown in Table 2-2.

EXAMPLE 9

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 7 wasused. The results are shown in Table 2-3.

EXAMPLE 10

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 8 wasused. The results are shown in Table 2-3.

EXAMPLE 11

The modification treatment and preparation of coated product werecarried out by the same methods as Example 2, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 8 wasused. The results are shown in Table 2-3.

EXAMPLE 12

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 9 wasused. The results are shown in Table 2-3.

EXAMPLE 13

The modification treatment and preparation of coated product werecarried out by the same methods as Example 6, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 8 wasused. The results are shown in Table 2-3.

EXAMPLE 14

The modification treatment and preparation of coated product werecarried out by the same methods as Example 7, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 8 wasused. The results are shown in Table 2-4.

EXAMPLE 15

The modification treatment and preparation of coated product werecarried out by the same methods as Example 8, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 8 wasused. The results are shown in Table 2-4.

COMPARATIVE EXAMPLE 6

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 9 wasused. The results are shown in Table 2-4.

COMPARATIVE EXAMPLE 7

The modification treatment and preparation of coated product werecarried out by the same methods as Example 1, and evaluation tests onphysical properties were carried out in the same manner, except that thepropylene-ethylene copolymer synthesized in Production Example 9 wasused. The results are shown in Table 2-4.

TABLE 2-1 Item Remarks Unit Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Ex. 7Ex. 8 Modification condition Charging Polymer Prod. Prod. Prod. Prod.Prod. Prod. Prod. Prod. amount Ex. 1 Ex. 2 Ex. 2 Ex. 3 Ex. 4 Ex. 1 Ex. 1Ex. 1 (wt part) 100 100 100 100 100 Monomer (wt part) Maleic Maleic Thesame The same The same Meth- HEMA HEMA anhydride anhydride as Ex. 1 asEx. 1 as Ex. 1 acrylic 25 25 20 50 Acid St 25 25 Solvent (wt part) 400400 400 400 400 DCPO (wt part) 8 7 2.5 2.5 2.5 Temperature (° C.) 132110 132 132 132 Graft ratio (wt %) 3.3 1.1 3.2 3.2 3.3 1.1 1.0 2.5Physical properties Solubility 0 0 0 0 0 0 0 0 Insoluble (%) <1 <1 <1 <1<1 <1 <1 <1 matter * Non- 0 0 0 0 0 0 0 0 tackiness Evaluation ofmodified polymer Base material Adhesiveness Ref. Ex. 1 (no./no.) 100/100100/100 100/100 100/100 100/100 100/100 100/100 100/100 Ref. Ex. 2100/100 100/100 100/100 100/100 100/100 100/100 100/100 100/100 GasoholRef. Ex. 1 (min) >90 77 >90 59 >90 >90 >90 >90 resistance Ref. Ex. 2 8532 75 30 >90 45 45 80 Water Ref. Ex. 1 (no./no.) 100/100 100/100 100/100100/100 100/100 100/100 100/100 100/100 resistance Ref. Ex. 2 100/100100/100 100/100 100/100 100/100 100/100 100/100 100/100 * Insolublematter (in 10 wt % toluene) Note: HEMA represents 2-hydroxyethylmethacrylate St represents styrene

TABLE 2-2 Comp. Comp. Comp. Comp. Comp. Item Remarks Unit Ex. 1 Ex. 2Ex. 3 Ex. 4 Ex. 5 Modification condition Charging Polymer Prod. Prod.UT-2115 XR110T CP-343-1 amount Ex. 5 Ex. 6 (wt part) The same The sameThe same The same Monomer (wt part) as Ex. 1 as Ex. 1 as Ex. 1 as Ex. 1Solvent (wt part) Initiator (wt part) Temperature (° C.) Graft ratio (wt%) 3.4 3.5 3.4 3.0 Physical properties Solubility X ◯ X X ◯ Insoluble(%) 96 <1 29.5 67.4 <1 matter * Non- ◯ X X ◯ ◯ tackiness Evaluation ofmodified polymer Base material Adhesive- Ref. (no./no.) 40/100 60/10040/100 80/100 ness Ex. 1 Ref.  0/100 20/100  0/100  0/100 Ex. 2 GasoholRef. (min) 10 15 >90 >90 resistance Ex. 1 Ref. 8 10 50 66 Ex. 2 WaterRef. (no./no.) 20/100 20/100 20/100 20/100 resistance Ex. 1 Ref.  0/100 0/100  0/100  0/100 Ex. 2 * Insoluble matter (in 10 wt % toluene)

TABLE 2-3 Item Remarks Unit Ex. 9 Ex. 10 Ex. 11 Ex. 12 Ex. 13Modification condition charging amount Polymer Prod. Prod. Prod. Prod.Prod. EX. 7 EX. 8 EX. 8 EX. 9 EX. 8 (wt part) The same The same The sameThe same The same monomer (wt part) as Ex. 1 as Ex. 1 as Ex. 2 as Ex. 1as Ex. 6 Solvent (wt part) Initiator (wt part) Temperature (° C.) Graftratio (wt %) 3.0 3.1 0.9 3.0 1.1 Physical properties solubility ◯ ◯ ◯ ◯◯ Insoluble matter* (%) <1 <1 <1 <1 <1 Non-tackiness ◯ ◯ ◯ ◯ ◯Evaluation of modified polymer Base material Adhesiveness Ref. Ex. 1(no./no.) 100/100 100/100 100/100 100/100 100/100 Gasohol resistanceRef. Ex. 1 (min) >90 >90 42 80 42 Water resistance Ref. Ex. 1 (no./no.)100/100 100/100 100/100 100/100 100/100 Insoluble matter* (in 10 wt %toluene)

TABLE 2-4 Comp. Comp. Comp. Item Remarks Unit Ex. 14 Ex. 15 Ex. 6 Ex. 7Ex. 8 Modification condition charging amount Polymer Prod. Prod. Prod.UT-2215 S4030 EX. 8 EX. 8 EX. 9 (wt part) The same The same The same Thesame The same monomer (wt part) as Ex. 7 as Ex. 8 as Ex. 1 as Ex. 1 asEx. 1 Solvent (wt part) Initiator (wt part) Temperature (° C.) Graftratio (wt %) 1.0 2.5 3.0 3.1 3.0 Physical properties solubility ◯ ◯ ◯ XX Insoluable matter* (%) <1 <1 <1 17.5 filtration was impossibleNon-tackiness ◯ ◯ X X ◯ Evaluation of modified polymer Base materialAdhesiveness Ref. Ex. 1 (no./no.) 100/100 100/100 40/100 60/100 0/100Gasohol resistance Ref. Ex. 1 (min) 40 80 15 15 50 Water resistance Ref.Ex. 1 (no./no.) 100/100 100/100 20/100 20/100 0/100 Insoluble matter*(in 10 wt % toluene)

As has been described in the foregoing, the invention renders possibleprovision of a novel propylene polymer which does not contain halogenssuch as chlorine and can add good adhesiveness and coating ability tocrystalline propylene polymer base materials. Thus, the invention hasindustrially great values.

While the invention has been described in detail and with reference tospecific embodiments thereof, it will be apparent to one skilled in theart that various changes and modifications can be made therein withoutdeparting from the gist and scope thereof.

This application is based on Japanese patent application No. 2001-336078filed on Nov. 1, 2001, the entire contents thereof being herebyincorporated by reference.

1. A propylene polymer, comprising: a propylene polymer main chainhaving a stereo-block structure containing an isotactic block, and aside chain containing a carboxylic acid group, an acid anhydride groupor a carboxylic acid ester group, wherein when said propylene polymer isdissolved in toluene to a concentration of 10% by weight at 25° C., theinsoluble matter is 1% by weight or less based on the total weight ofthe polymer.
 2. The propylene polymer according to claim 1, wherein thepropylene main chain comprises a propylene and ethylene component at theratio of 95<[Propylene]≦100 (weight %) and 5>[Ethylene]≧0 (weight %). 3.The propylene polymer according to claim 1, wherein the propylenepolymer main chain is produced by a single site catalyst.
 4. Thepropylene polymer according to claim 1, wherein when the propylenepolymer main chain is dissolved in heptane to a concentration of 10% byweight at 98° C., the insoluble matter is 1% by weight or less based onthe total weight of the polymer.
 5. The propylene polymer according toclaim 1, wherein the propylene polymer main chain has a weight averagemolecular weight Mw of 5,000 or more and 200,000 or less when measuredby GPC.
 6. The propylene polymer according to claim 1, wherein adistinctive peak corresponding to a crystal melting calorie of 1 joule/gor more at a melting point (Tm) measured by DSC is not present in thepropylene polymer main chain.
 7. The propylene polymer according toclaim 3, wherein the single site catalyst is a C₁-symmetricansa-metallocene compound having a transition metal-containing bridgegroup.
 8. The propylene polymer according to claim 1, whereinsubstantially all components of the propylene polymer main chain and/orpropylene polymer are eluted at 60° C. or less when subjected totemperature rising elution fractionation with o-dichlorobenzene.
 9. Thepropylene polymer according to claim 1, wherein the side chaincarboxylic acid group, acid anhydride group or carboxylic acid estergroup in claim 1 is introduced into the propylene polymer main chain byallowing a polymerizable compound to undergo graft copolymerization. 10.The propylene polymer according to claim 9, wherein the polymerizablecompound is an unsaturated carboxylic acid compound comprising anunsaturated carboxylic acid having from 3 to 25 carbon atoms, an acidanhydride thereof or an ester thereof.
 11. The propylene polymeraccording to claim 10, wherein the unsaturated carboxylic acid compoundcomprising an unsaturated carboxylic acid having from 3 to 25 carbonatoms, an acid anhydride thereof or an ester thereof is maleicanhydride.
 12. The propylene polymer according to claim 1 having thefollowing characteristics (a) and (b); (a) when said propylene polymeris dissolved in toluene to a concentration of 10% by weight at 25° C.,the insoluble matter is 1% by weight or less based on a total weight ofsaid polymer, and (b) an adhesiveness of said propylene polymer asmeasured by an adhesion test to a polypropylene base material is 50/100or more; wherein said adhesion test is a cross-cut tape method.
 13. Anadhesion composition prepared by dissolving 1 weight part or more of thepropylene polymer according to claim 1 in a solvent having a solubilityparameter of 11 (cal/cm³)^(1/2) or less.
 14. An adhesion compositionprepared by dissolving 1 weight part or more of the propylene polymeraccording to claim 12 in a solvent having a solubility parameter of 11(cal/cm³)^(1/2) or less.
 15. An adhesive for an olefin polymer havingcrystallinity, which comprises the propylene polymer according toclaim
 1. 16. An adhesive for an olefin polymer having crystallinity,which comprises the propylene polymer according to claim
 12. 17. Anadhesive for an olefin polymer having crystallinity, which comprises thecomposition according to claim
 13. 18. An adhesive for an olefin polymerhaving crystallinity, which comprises the composition according to claim14.
 19. A method of making a propylene polymer, comprising: polymerizingpropylene or a mixture of propylene and ethylene in the presence of asingle site catalyst which is a C₁-symmetric ansa-metallocene compoundhaving a transition metal-containing bridge group, thereby obtaining apropylene polymer main chain having a stereo-block structure containingan isotactic block, and graft-copolymerizing said propylene polymer mainchain with a polymerizable monomer containing a carboxylic acid group,an acid anhydride group or a carboxylic acid ester group; to obtain aside chain containing a carboxylic acid group, an acid anhydride groupor a carboxylic acid ester group, wherein when said propylene polymer isdissolved in toluene to a concentration of 10% by weight at 25° C., theinsoluble matter is 1% by weight or less based on the total weight ofthe polymer.
 20. The method according to claim 19, wherein saidpropylene polymer main chain is a propylene homopolymer or apropylene-ethylene copolymer having an ethylene content of less than 5%by weight, based on a total weight of said main chain.
 21. The methodaccording to claim 19, wherein a grafted amount of at least one graftpolymerization unit obtained from said polymerizable monomer containinga carboxylic acid group, an acid anhydride group or a carboxylic acidester group is 0.01 to 25% by weight.
 22. The method according to claim19, wherein said C₁-symmetric ansa-metallocene compound having atransition metal-containing bridge group is a C₁-symmetricansa-metallocene compound of a crosslinked group IV transition metalcompound having a conjugated five-membered ring ligand.
 23. A propylenepolymer, comprising: a propylene polymer main chain having astereo-block structure containing an isotactic block, and a side chaincontaining a carboxylic acid group, an acid anhydride group or acarboxylic acid ester group, wherein when said propylene polymer isdissolved in toluene to a concentration of 10% by weight at 25° C., theinsoluble matter is 1% by weight or less based on the total weight ofthe polymer; wherein the propylene polymer main chain is produced by asingle site catalyst; and wherein the single site catalyst is aC₁-symmetric ansa-metallocene compound having a transitionmetal-containing bridge group.